CN109761263A - The cuprous oxide crystal preparation method of morphology controllable - Google Patents
The cuprous oxide crystal preparation method of morphology controllable Download PDFInfo
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- CN109761263A CN109761263A CN201910198691.3A CN201910198691A CN109761263A CN 109761263 A CN109761263 A CN 109761263A CN 201910198691 A CN201910198691 A CN 201910198691A CN 109761263 A CN109761263 A CN 109761263A
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- cuprous oxide
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Abstract
The cuprous oxide crystal preparation method of morphology controllable, comprising: the aqueous solution comprising copper ion and halide anion is provided in water-bath container；NaOH solution is added dropwise in water-bath container；Ascorbic acid is added dropwise in water-bath device again；And the cuprous oxide crystal of required pattern will be obtained after product centrifugation, washing, drying, wherein the bath temperature of water-bath device remains 50~60 DEG C；And required pattern is regulated and controled by selection halide anion type.The present invention is in single aqueous phase solvent system, the controllable preparation to cube, cuboctahedron and these three octahedra different-shape cuprous oxide crystals only can be realized by regulation this unitary variant of halide anion, and product crystal structural integrity, pattern are uniform, with high purity.
Description
Technical field
The present invention relates to the preparation methods of cuprous oxide crystal.
Background technique
Cuprous oxide is a kind of with visible light-responded p-type semiconductor material, has cheap, rich reserves, ring
The advantages that border is friendly, in the technical fields such as solar battery, photochemical catalyzing, organic pollutant in wastewater by photocatalysis
With important application value.Cuprous oxide crystal pattern is numerous, the soluble removal in acid or alkaline environment, often by as mould
Plate is used to synthesize the nanoparticle with specific morphology.In addition, a large number of studies show that the electronic structure of material, surface energy and chemistry
Reactivity depends not only on the type of substance, and is largely dependent upon the crystal habit and surface topography of material.
Therefore, simple controllable cuprous oxide crystal preparation method is developed to the synthesis of specific morphology template and exposes high activity crystal face
Catalyst research is of great significance.
At present the preparation method of cuprous oxide crystal mainly have high-temperature sintering process, electrochemical process, hydrothermal/solvent thermal method and
Liquid phase reduction.Wherein, liquid phase reduction is easy to operate, low in cost, is easy to concentration, reaction temperature by adjusting predecessor
The cuprous oxide of the synthetic parameters controlledly synthesis such as degree, reaction time different-shape, is most common method.Patent
CN107954463A disclose it is a kind of first reacted using copper acetate dihydrate and sodium hydroxide, be then with lauryl sodium sulfate
Surfactant and stabilizer, it is brilliant that cuprous nano is made in the deionized water and hydrazine hydrate aqueous solution for adding different volumes ratio
The method of cube and hollow polyhedral.Patent CN109095492A is disclosed using a certain amount of cupric salt and structure directing
The dissolution of agent boric acid forms mixed solution in deionized water, appropriate reducing agent ascorbic acid is then added, product is centrifuged, is washed
After washing, drying, the method that obtains octahedra uniform morphology cuprous oxide micron crystalline substance.
In traditional liquid phase reduction, solvent is generally binary or multicomponent system, generally for regulation product morphology and
The cuprous oxide for avoiding precipitating from being formed is reunited, and needs to control lower pre-reaction material concentration and a certain amount of surface is added
Activating agent.Although these means realize the regulation to cuprous oxide pattern to a certain extent, preparation and production are also increased
The difficulty of object cleaning, and concentration is low, time-consuming and is difficult to produce in enormous quantities, more importantly the introducing meeting of surfactant
The serious activity for reducing cuprous oxide in catalytic applications.
Summary of the invention
An object of the present invention is to provide a kind of simple and practical and morphology controllable cuprous oxide crystal preparation method.
According to the first aspect of the invention, a kind of preparation method of the cuprous oxide crystal of morphology controllable is provided, is wrapped
It includes:
The aqueous solution comprising copper ion and halide anion is provided in water-bath container, wherein copper ion and halogen yin
The molar ratio of ion is about 1:2；
NaOH solution is added dropwise in water-bath container, or so reaction half an hour, wherein added NaOH and copper ion
Molar ratio be about 20:1；
Ascorbic acid is added dropwise in water-bath device again, reacts or so hour, wherein added ascorbic acid and copper
The molar ratio of ion is about 6:1；And
The cuprous oxide crystal of required pattern will be obtained after product centrifugation, washing, drying,
Wherein, the bath temperature of water-bath device remains 50~60 DEG C；And
Regulate and control required pattern by selection halide anion type:
By selecting Cl-Cuprous oxide crystal pattern is adjusted to cube as halide anion；
By selecting Br-Cuprous oxide crystal pattern is adjusted to cuboctahedron as halide anion；
By selecting I-Cuprous oxide crystal pattern is adjusted to octahedron as halide anion.
Preparation method according to the present invention, halide anion may include Cl-、Br-And I-One of or more.
The highly basic such as potassium hydroxide substitution sodium hydroxide also can be used in alternate embodiment according to the present invention.
According to another aspect of the present invention, a kind of cuprous oxide crystal template is additionally provided, is prepared according to the above method.
Compared with prior art, the present invention has following remarkable result:
1, in single aqueous phase solvent system, only by regulate and control this unitary variant of halide anion can be realized to cube
Body (Cl-), cuboctahedron (Br-) and octahedron (I-) these three different-shape cuprous oxide crystals controllable preparation, and product
Crystal structure is complete, pattern is uniform, with high purity.
2, present invention process is simple, mild condition, reaction time are short, low to laboratory apparatus precision requirement, to product shape
The controllability of looks is high, reproducible, is suitble to scale industrial production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of cube cuprous oxide crystal prepared in accordance with the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of cuboctahedron cuprous oxide crystal prepared in accordance with the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of octahedra cuprous oxide crystal prepared in accordance with the present invention；And
Fig. 4 is the XRD material phase analysis figure of three kinds of pattern cuprous oxide crystals prepared in accordance with the present invention.
Specific embodiment
Preparation method of the invention is further described in detail below by specific embodiment and attached drawing, but its
It is not intended to restrict the invention.
Embodiment 1: selection chloride ion regulation prepares cube cuprous oxide crystal
(1) 55 DEG C of water-bath temperature are set, the NaOH solution 10mL of 2mol/L is added drop-wise to 100mL 0.01mol/L's
CuCl2In aqueous solution, it is stirred to react 30min.
(2) to reducing agent ascorbic acid 10mL, the water-bath 1h of mixed solution and dripping 0.6mol/L, by product from
The heart, washing, drying are to get the cuprous oxide crystal for arriving cube pattern.
Embodiment 2: selection bromide ion regulation prepares cuboctahedron cuprous oxide crystal
(1) 55 DEG C of water-bath temperature are set, the NaOH solution 10mL of 2mol/L is added drop-wise to 100mL 0.01mol/L's
CuBr2In aqueous solution, it is stirred to react 30min.
(2) to reducing agent ascorbic acid 10mL, the water-bath 1h of mixed solution and dripping 0.6mol/L, by product from
The heart, washing, drying are to get the cuprous oxide crystal for arriving cuboctahedron pattern.
Embodiment 3: selection iodide ion regulation prepares octahedra cuprous oxide crystal
(1) 55 DEG C of water-bath temperature are set, the NaOH solution 10mL of 2mol/L is added drop-wise to 100mL 0.01mol/L's
In CuI aqueous solution, it is stirred to react 30min.
(2) to reducing agent ascorbic acid 10mL, the water-bath 1h of mixed solution and dripping 0.6mol/L, by product from
The heart, washing, drying are to get the cuprous oxide crystal for arriving shape of octahedron.
Fig. 1-3 is respectively the scanning electron microscope (SEM) photograph of cuprous oxide crystal prepared by embodiment 1-3, by regulating and controlling reaction system
In halide anion type, the cuprous oxide crystal of cube, cuboctahedron and octahedra three kinds of different-shapes has been made,
And crystal structure is complete, pattern is uniform.Fig. 4 is then the XRD material phase analysis figure of cuprous oxide crystal prepared by embodiment 1-3,
Position standard diffraction peak (JPCDS05-0667) of cuprous oxide crystal diffraction maximum obtained and cuprous oxide is completely the same, they
2 θ angles be respectively 29.5 °, 36.4 °, 42.3 °, 52.4 °, 61.3 °, 69.6 °, 73.5 ° and 77.3 °, it is sub- to respectively correspond oxidation
(110), (111), (200), (211), (220), (310), (311) and (222) crystal face of copper.
Claims (3)
1. a kind of preparation method of the cuprous oxide crystal of morphology controllable, comprising:
The aqueous solution comprising copper ion and halide anion is provided in water-bath container, wherein copper ion and halide anion
Molar ratio be about 1:2；
NaOH solution is added dropwise in water-bath container, reaction or so half an hour, wherein added NaOH and copper ion rub
You are than being about 20:1；
Ascorbic acid is added dropwise in water-bath device again, reacts or so hour, wherein added ascorbic acid and copper ion
Molar ratio be about 6:1；And
The cuprous oxide crystal of required pattern will be obtained after product centrifugation, washing, drying,
Wherein, the bath temperature of water-bath device remains 50~60 DEG C；And
Regulate and control required pattern by selection halide anion type:
By selecting Cl-Cuprous oxide crystal pattern is adjusted to cube as halide anion；
By selecting Br-Cuprous oxide crystal pattern is adjusted to cuboctahedron as halide anion；
By selecting I-Cuprous oxide crystal pattern is adjusted to octahedron as halide anion.
2. preparation method according to claim 1, wherein halide anion includes Cl-、Br-And I-One of or more
It is a variety of.
3. a kind of cuprous oxide crystal template, preparation method preparation according to claim 1 or 2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114250074A (en) * | 2020-09-24 | 2022-03-29 | 浙江大学 | Preparation method of quantum dot, shape conversion method of quantum dot, quantum dot and composition thereof |
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| WO2011010663A1 (en) * | 2009-07-22 | 2011-01-27 | 日本化学工業株式会社 | Particles coated with cuprous oxide, method for producing same, and antifouling coating material containing the particles coated with cuprous oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114250074A (en) * | 2020-09-24 | 2022-03-29 | 浙江大学 | Preparation method of quantum dot, shape conversion method of quantum dot, quantum dot and composition thereof |
| CN114250074B (en) * | 2020-09-24 | 2023-04-28 | 浙江大学 | Quantum dot preparation method, quantum dot shape conversion method, quantum dot and quantum dot composition |
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