CN103043703A - Preparation method of hollow Cu2O cubic box - Google Patents

Preparation method of hollow Cu2O cubic box Download PDF

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Publication number
CN103043703A
CN103043703A CN2013100028337A CN201310002833A CN103043703A CN 103043703 A CN103043703 A CN 103043703A CN 2013100028337 A CN2013100028337 A CN 2013100028337A CN 201310002833 A CN201310002833 A CN 201310002833A CN 103043703 A CN103043703 A CN 103043703A
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preparation
copper oxide
hollow
reductive agent
red copper
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CN103043703B (en
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刘超
吴洁
纪秀杰
张兴华
胡龙
李兰兰
唐成春
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Hebei University of Technology
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Hebei University of Technology
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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

The preparation method of hollow Red copper oxide cube box
Technical field
Technical scheme of the present invention belongs to the synthetic field of hollow structure functional materials technology, is specially a kind of method at the standby hollow Red copper oxide cube box of the auxiliary lower backflow legal system of tensio-active agent.
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 are 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, because the difference of preparation method and granular size, can show as Huang, orange, the multiple color such as red or purple.
Red copper oxide is having potential application as a kind of p-type semiconductor material with unique light, magnetism characteristic aspect solar energy converting, electronics, magnetic storing unit, bio-sensing and the catalysis.The Red copper oxide band gap width is 2.1eV, and exciton can transmit in monocrystalline continuously, makes it have higher specific absorbance, becomes the important materials of making photovoltaic converter.In addition, because 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 recently research 2The submicron particles of O can be used for the negative material of lithium cell; The Red copper oxide of submicron order has special photocatalytic activity, can generate hydrogen and oxygen by photodissociation water under the visible light effect, and this exploitation for 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 with its unique calorifics, magnetics, optics, electricity and surface properties and its potential utilization at aspects such as catalyzer, sorbent material, medicament transport, optical imagery, photonic crystal, advanced low-k materials and sound-proof materials.Along with extensively carrying out of hollow structure research, corresponding nanometer ball, nanocubes, octahedral hollow structure also prepare recently.
Kuo etc. under the condition that NaOH solution exists, use NH in the Surfactant SDS system 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, cause acid etching by adding ethanol in this system and prepared another { the nanometer skeleton construction of 110} crystal face part hollow out (C.H.Kuo, M.H.Huang.Fabricationof truncated rhombic dodecahedral Cu 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 2The O hollow ball, and along with the increase of CTAB concentration, the 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. adopt N take sodium lauryl sulphate-polyvinylpyrrolidone soft matter cluster as template 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 the 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).The Gao Hongjun group is done template, CuSO with tensio-active agent cetyl trimethyl ammonia bromide (CTAB) 4Be the Cu source, obtained Cu with the xitix reduction 2The nano-hollow cubes of O (H.R.Zhang, C.M.Shen, S.T.Chen, Z.C.Xu, et al.Nanotechnology, 2005,16:267-272).The people such as Luo adopt liquid phase reduction in the presence of nonionogenic tenside Triton X-100, use Reduction of Glucose CuCl 2Obtain Cu 2O solid cubes gradually cavitation to have prepared the length of side be Cu about 200nm 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 with PdCl 2Be incorporated in the film solution, make reductive agent with glucose, the Cu that obtained monocrystalline in 3 hours 75 ℃ of lower ageings 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, and auxiliary lower at sodium laurylsulfonate (SDS), in ethylene glycol-water or ethanol-water system, prepared hollow Cu with circumfluence method 2O cube of box, and its size is about 1 micron, has larger internal space.
The present invention solves this technical problem the technical scheme that adopts:
A kind of preparation method of 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, in addition sodium laurylsulfonate and reductive agent are dissolved in the alcohol, make sodium laurylsulfonate-reductive agent-alcoholic solution, its concentration is that every milliliter of alcohol contains 0.0125～0.1 gram sodium laurylsulfonate and 0.0078～0.0675 gram reductive agent, gets 20 parts of copper salt solutions and mixes with 40 parts of sodium laurylsulfonate-reductive agent-alcoholic solutions, 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 the water, making concentration is the precipitant solution of 0.16～0.269 gram precipitation agent/ml water, gets 10 parts, adds 20～80 parts alcohol again, is mixed with precipitation agent-alcohol-water mixed solution, stand-by;
(3) with in the flask in the mixing solutions adding step (1) of preparation in the step (2), be warming up to reflux temperature under the nitrogen protection, back flow reaction 2～4 hours stops to stir and heating;
(4) products therefrom of upper step was at room temperature left standstill 0～15 hour again, obtain brick-red precipitation, then washing again through suction filtration, with the brick-red precipitation vacuum drying of gained, obtains hollow Red copper oxide cube box powder.
The umber of said components is volume parts, and used volume unit is identical in each step.
Mantoquita described in the top step (1) is cupric chloride, copper sulfate or neutralized verdigris;
Alcohol described in top step (1) and (2) is ethylene glycol or ethanol.
When the reductive agent in the top step (1) was glucose, reductive agent was 0.045～0.0675 gram glucose/milliliter alcohol with the proportioning of alcohol;
When the reductive agent in the top step (1) was S-WAT, reductive agent was 0.0315～0.0378 gram S-WAT/milliliter alcohol with the proportioning of alcohol;
When the reductive agent in the top step (1) was hydrazine hydrate, reductive agent was 0.0078～0.0118 gram hydrazine hydrate (massfraction is 80%)/milliliter alcohol with the proportioning of alcohol;
Precipitation agent described in the top step (2) is sodium hydroxide or potassium hydroxide;
When the precipitation agent described in the top step (2) was sodium hydroxide, the concentration of precipitant solution was 0.16～0.192 gram sodium hydroxide/ml water;
When the precipitation agent described in the top step (2) was potassium hydroxide, the concentration of precipitant solution was 0.224～0.269 gram potassium hydroxide/ml water;
The invention has the beneficial effects as follows:
1. the rib of the resulting hollow Red copper oxide cube box of the inventive method 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, the 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 the crystallinity that obtains Red copper oxide is 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 raw material cupric chloride, copper sulfate, the neutralized verdigris that adopt of the present invention; 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, and is cheap and easy to get.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the XRD spectra of hollow Red copper oxide cube box among the embodiment 1.
Fig. 2 is the SEM photo of hollow Red copper oxide cube box among the embodiment 1.
Embodiment
Embodiment 1
(1) the 0.02mol cupric chloride is dissolved in the 20mL water, in addition 1g sodium laurylsulfonate and 2.4g glucose are dissolved in the 40mL ethylene glycol, make sodium laurylsulfonate-glucose-ethylene glycol mixing solutions, then it is mixed with copper salt solution, in the flask of adding with reflux, stir, stand-by.
(2) with the 1.6g dissolution of sodium hydroxide in 10mL water, add again 20mL ethylene glycol, be mixed with sodium hydroxide-ethylene glycol-water mixed solution, stand-by.
(3) with in the flask in the mixing solutions adding step (1) of preparation in the step (2), be warming up to reflux temperature under the nitrogen protection, back flow reaction 3h stops to stir and heating;
(4) again products therefrom of upper step is at room temperature left standstill 15h, obtain brick-red precipitation, then wash 3 times, again through suction filtration, brick-red being deposited in 60 ℃ the vacuum drying oven of gained dried, 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 the 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 refluxing is changed respectively the operation in the step (3) among the embodiment 1 into 2h, 2.5h, 3.5h, 4h, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 6
With step (1) C among the embodiment 1 6H 12O 6Consumption change 1.8g into, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 7
With step (1) C among the embodiment 1 6H 12O 6Consumption change 2.7g into, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 8
Change the consumption of step (1) SDS among the embodiment 1 into 0.5g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 9
Change the consumption of step (1) SDS among the embodiment 1 into 4g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 10
Change the consumption of step (2) NaOH among the embodiment 1 into 1.92g, other steps obtain product with embodiment 1,0.65g with embodiment 1.
Embodiment 11
(1) 0.02mol copper sulfate is dissolved in the 20mL water, in addition 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, in the flask of adding with reflux, stir, stand-by.
(2) 2.24g potassium hydroxide is dissolved in the 10mL water, adds again 20mL ethylene glycol, be mixed with potassium hydroxide-ethylene glycol-water mixed liquid, stand-by.
(3) with in the flask in the mixing solutions adding step (1) of preparation in the step (2), be warming up to reflux temperature under the nitrogen protection, back flow reaction 2h stops to stir and heating.
(4) again products therefrom of upper step is at room temperature left standstill 0h, obtain brick-red precipitation, then it is washed three times with deionized water, again through suction filtration, brick-red being deposited in 60 ℃ the vacuum drying oven of gained dried, obtain product hollow Red copper oxide cube box powder 0.63g.
Embodiment 12
Change the consumption of step (2) KOH among the embodiment 11 into 2.69g, other steps obtain product with embodiment 11 with embodiment 11.
Embodiment 13
Change step (1) cupric chloride among the embodiment 1 into neutralized verdigris, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 14
Change the amount of step (2) ethylene glycol among the embodiment 1 into 80mL, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 15
Change the amount of step (2) ethylene glycol among the embodiment 11 into 80mL, other steps obtain product with embodiment 11 with embodiment 11.
Embodiment 16
Change the amount of step (2) ethylene glycol among the embodiment 13 into 80mL, other steps obtain product with embodiment 13 with embodiment 13.
Embodiment 17
Change step (1) glucose among the embodiment 1 into S-WAT 1.26g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 18
Change step (1) glucose among the embodiment 1 into S-WAT 1.512g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 19
Change step (1) glucose among the embodiment 1 into hydrazine hydrate (massfraction is 80%) 0.312g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 20
Change step (1) glucose among the embodiment 1 into hydrazine hydrate (massfraction is 80%) 0.472g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 21-40
Change step (1), (2) ethylene glycol among the embodiment 1-20 into ethanol, other steps obtain product with embodiment 1-20 with embodiment 1-20.

Claims (9)

1. the preparation method of a hollow Red copper oxide cube box is characterized by and 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, in addition sodium laurylsulfonate and reductive agent are dissolved in the alcohol, make sodium laurylsulfonate-reductive agent-alcoholic solution, its concentration is that every milliliter of alcohol contains 0.0125～0.1 gram sodium laurylsulfonate and 0.0078～0.0675 gram reductive agent, gets 20 parts of copper salt solutions and mixes with 40 parts of sodium laurylsulfonate-reductive agent-alcoholic solutions, 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 the water, making concentration is the precipitant solution of 0.16～0.269 gram precipitation agent/ml water, gets 10 parts, adds 20～80 parts alcohol again, is mixed with precipitation agent-alcohol-water mixed solution, stand-by;
(3) with in the flask in the mixing solutions adding step (1) of preparation in the step (2), be warming up to reflux temperature under the nitrogen protection, back flow reaction 2～4 hours stops to stir and heating;
(4) products therefrom of upper step was at room temperature left standstill 0～15 hour again, obtain brick-red precipitation, then washing again through suction filtration, with the brick-red precipitation vacuum drying of gained, obtains hollow Red copper oxide cube box powder;
The umber of said components is volume parts, and used volume unit is identical in each step.
2. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, it is characterized by the mantoquita described in the described step (1) is cupric chloride, copper sulfate or neutralized verdigris.
3. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, it is characterized by the alcohol described in described step (1) and (2) is ethylene glycol or ethanol.
4. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in the described step (1) and being glucose, reductive agent is that 0.045～0.0675 gram glucose/milliliter is pure with the proportioning of alcohol.
5. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in the described step (1) and being S-WAT, reductive agent is that 0.0315～0.0378 gram S-WAT/milliliter is pure with the proportioning of alcohol.
6. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in the described step (1) and being hydrazine hydrate, reductive agent is that 0.0078～0.0118 gram hydrazine hydrate (massfraction is 80%)/milliliter is pure with the proportioning of alcohol.
7. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, it is characterized by the precipitation agent described in the described step (2) is sodium hydroxide or potassium hydroxide.
8. 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 the described step (2) and being sodium hydroxide, the concentration of precipitant solution is 0.16～0.192 gram sodium hydroxide/ml water.
9. 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 the described step (2) and being potassium hydroxide, the concentration of precipitant solution is 0.224～0.269 gram potassium hydroxide/ml water.
CN201310002833.7A 2013-01-05 2013-01-05 Preparation method of hollow Cu2O cubic box Expired - Fee Related CN103043703B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104591257A (en) * 2015-01-12 2015-05-06 广东光华科技股份有限公司 Preparation method of cubic micro/nano cuprous oxide powder
CN107840361A (en) * 2016-09-20 2018-03-27 天津工业大学 A kind of preparation method of cupric oxide microballoon
CN107900374A (en) * 2015-12-28 2018-04-13 重庆文理学院 A kind of preparation method of the good cube platinum nano material of uniformity
CN107954463A (en) * 2017-12-07 2018-04-24 青岛大学 A kind of preparation method of cuprous nano crystalline substance cube and hollow polyhedral
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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Publication number Priority date Publication date Assignee Title
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
CN102350499A (en) * 2011-09-28 2012-02-15 河北工业大学 Cu/Cu2O core-shell composite microsphere and preparation method thereof
CN102557106A (en) * 2012-01-12 2012-07-11 淮阴师范学院 Preparation method of cuprous oxide hollow nanometer cubes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102350499A (en) * 2011-09-28 2012-02-15 河北工业大学 Cu/Cu2O core-shell composite microsphere and preparation method thereof
CN102557106A (en) * 2012-01-12 2012-07-11 淮阴师范学院 Preparation method of cuprous oxide hollow nanometer cubes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104591257A (en) * 2015-01-12 2015-05-06 广东光华科技股份有限公司 Preparation method of cubic micro/nano cuprous oxide powder
CN107900374A (en) * 2015-12-28 2018-04-13 重庆文理学院 A kind of preparation method of the good cube platinum nano material of uniformity
CN107840361A (en) * 2016-09-20 2018-03-27 天津工业大学 A kind of preparation method of cupric oxide microballoon
CN107954463A (en) * 2017-12-07 2018-04-24 青岛大学 A kind of preparation method of cuprous nano crystalline substance cube and hollow polyhedral
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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