CN105129835B - Hexacosahedral cuprous oxide nanometer particle preparation method - Google Patents
Hexacosahedral cuprous oxide nanometer particle preparation method Download PDFInfo
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- reducing agent
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
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- 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 present invention discloses a hexacosahedral cuprous oxide nanometer particle preparation method, which comprises: dissolving an inorganic copper salt in a solvent, adding an additive, adding an alkaline substance, adding a reducing agent, carrying out a reaction for 0.5-6 h at a temperature of 30-90 DEG C, carrying out centrifugation separation on the obtained reaction solution by controlling the rotation speed at 6000-8000 r/min, washing the obtained precipitate with deionized water until the pH value of the washing liquid is neutral, and drying by controlling the temperature at 40-80 DEG C so as to obtain the hexacosahedral cuprous oxide nanometer particles. According to the present invention, the hexacosahedral cuprous oxide nanometer particles have the special appearance, have more crystal surface exposing for photocatalysis, and can be used for photocatalytic degradation of organic pollutants, and the preparation method has characteristics of low cost and simple and controllable synthesis pathway, and is suitable for mass production.
Description
Technical field
The invention belongs to field of inorganic nano material, is related to a kind of cuprous nano particle, specifically a kind of two
The preparation method of ten hexahedron cuprous nano particles.
Background technology
Nano material has the characteristic for differing markedly from block materials and individual molecule:Skin effect, bulk effect, quantum
Dimensional effect and macroscopical tunnel-effect etc..Either in theory or in actual application aspect, with uniform particle size and shape
The inorganic nanoparticles of shape all cause the great interest of people.The synthesis of regular shape nanostructured is in photon, nanometer electricity
There is great using value in the fields such as son, information storage, catalysis and biology sensor.
Cuprous oxide (Cu20) be it is rare can be by a kind of typical p-type semiconductor material of excited by visible light, it can bandwidth
Spend for 2.17eV.Due to its excellent physical and chemical performance, in the potential using value of every field people are gradually caused
Attention.Cu20 have good gas sensing property and piezoelectricity, can by wavelength for 400-800 nm excited by visible light;Polycrystalline state
Cu20 have good stability, can Reusability without being reduced to Cu or being oxidized to CuO;In addition, Cu20 is nontoxic, reserves
Abundant, preparation cost is relatively low, cheap, and its purposes in each field gradually obtains the research and development of people, and in people
Daily life in play indispensable effect.Such as：（1）In recent years, cuprous catalysis cross-coupling reaction oneself become popular
Research direction, and be widely used in the middle of organic synthesis, bioactive molecule preparation and industrial production.（2）Cu20 has because of it
Inexpensively, abundance is big, easily prepare, absorb visible ray, band gap can reconcile the characteristics such as low toxicity, have in photocatalysis field and extensively should
With.（3）This its industrial use as important Inorganic Chemicals of cuprous oxide is very wide, and industrial products are applied to more than 90%
The antifouling paint field of ship, this coating can reach antifouling purpose by seawater as anti-fouling agent to its dissolution.
（4）Using the oxide-metal composite prepared based on cuprous oxide, can be used as the application of non-burning anode and electrolysis process
In.As cuprous oxide pattern controls the continuous development of preparation method research, its using value also result in extensive concern, near
Nian Lai, using distinct methods the controllable Cu of pattern and size is prepared2The 0 nanocrystalline heat for having become various countries researcher concern
Point.
2005, Choi groups it is once detailed to have studied electrolyte temperature, decomposition voltage, current density, electrolyte dense
Degree, reaction time and protective agent are to Cu2The pattern of 0 crystal growth affects.This group also reports and uses three-electrode system, uses SDS
（Lauryl sodium sulfate）, crystal face is adsorbed in from excellent as the surfactant of anion, exist in the pH scopes of control system
(3.4,3.5,3.7,3.9) and to obtain crystalline form octahedra for cube, beveling cube, octahedra and rescinded angle.Guo is also reported
In the system without template and surfactant, by adjusting voltage in 0.6V, cube Cu can be obtained20, voltage is in 0.7V
Cu is obtained20 nanosphere.Li etc. also once reported that ([MEIN]+[at room temperature, electrolysis obtained Cu to ESD to hydrophilic ionic liquids20.
Control ionic liquid content can finally give the Cu such as cube, beveling cube, octahedron, spherical at (0-0.08%)20.
Chen etc. is reactant with ammoniacal liquor and copper acetate, and in the autoclave of polytetrafluoroethylene kettle lining 150- is heated
245 °C, 5-72 h are reacted, long cylindrical particle can be obtained, and study its mechanism of nucleation.The triethanolamine such as Li, acetic acid acid copper
Be raw material with water, in autoclave, after being heated to 160 DEG C and continuing, generate by centrifugation, washing and after being dried octahedron and
The Cu of octahedra nucleocapsid shape20 particle.Zeng etc. substitutes the hydro-thermal reaction method of water using DMF, is controlling final reaction time system
For Cu20 hollow cube and hollow ball.Jiao groups PEG-200 is that solvent obtains size between 50nm-200nm
Cu20 cube.
Zhu Haitao has prepared hollow sphere made from cuprous oxide using polyvinylpyrrolidone.Tan Qiang is waited prepared using urea by force
Carry out octahedra cuprous oxide.Tao Feifei etc. has prepared Emission in Cubic cuprous oxide using anhydrous sodium acetate and DEXTROSE ANHYDROUS.
Li Yadong is copper source using copper nitrate, and potassium borohydride is reducing agent, under oil bath, obtains the nanometer of 250nm or so
Ball, but surface smoother, surface area thus specific surface area is relatively small.
In theory, the cuprous oxide with particular crystal plane is conducive to improving its photocatalysis performance.
In sum, the cuprous oxide with different crystal faces is different, institute for the efficiency of photocatalytic degradation organic matter
There is larger benefit to practical application with the cuprous oxide for possessing special crystal face, therefore explore and be of relatively low cost, operate letter
Single, the cuprous nano material with special crystal face and preparation method are significant.And prepared by this method 26
Face body cuprous oxide has various crystal faces, wherein there is specific crystal face to have potential application in photocatalytic degradation organic matter field
Prospect.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of 20 hexahedron cuprous nano grains
The preparation method of son, the preparation method of described this 20 hexahedron cuprous nano particle solves of the prior art
Prepare method high cost, the technical problem of complex process of 20 hexahedron cuprous nano particles.
The invention provides a kind of preparation method of 20 hexahedron cuprous nano particle, inorganic mantoquita is dissolved in
In solvent, additive is added, be subsequently adding alkaline matter, be subsequently added after reducing agent is well mixed, under the conditions of 30-90 DEG C,
Reaction 0.5-6h is carried out, the reactant liquor of gained is controlled into rotating speed and is centrifuged for 6000-8000r/min, the precipitation of gained
The pH being washed with deionized to eluate is neutrality, then controls temperature and is dried for 40-80 DEG C, that is, obtain 26 faces
Body cuprous nano particle；
The material ratio of above-mentioned inorganic mantoquita used, solvent, additive, alkaline matter and reducing agent is 0.001-
0.1mol：5-200ml：0.005-4g:0.05-0.4g:0.05-1g；
Wherein, described inorganic mantoquita is copper nitrate, copper sulphate or copper chloride；
Described solvent is one kind of water, ethanol, methyl alcohol or ethylene glycol and the mixture of two or more compositions；
Described additive is one kind of hydrochloric acid, ethylenediamine or sodium citrate and the mixture of two or more compositions；
Described alkaline matter is that NaOH, potassium hydroxide, ammoniacal liquor or sodium acid carbonate be a kind of and two or more compositions
Mixture；
Described reducing agent is that formic acid, acetaldehyde, glucose or ascorbic acid be a kind of and mixing of two or more compositions
Thing.
Further, described inorganic mantoquita is copper nitrate, described aqueous solvent, and described additive is ethylenediamine, institute
The alkaline matter stated is sodium acid carbonate, and described reducing agent is glucose.
Further, a kind of preparation method of above-mentioned 20 hexahedron cuprous nano particle, comprises the steps:
（1）, inorganic mantoquita be dissolved in solvent obtain inorganic copper salt solution；
（2）, in step（1）Additive is added in the inorganic copper salt solution of gained, 10-20min is stirred, alkaline matter is added
Stirring 10-20min, adds reducing agent, after being uniformly mixed, under the conditions of 30-90 DEG C, carries out reaction 0.5-6h；
（3）, step（2）After reaction terminates, the reactant liquor of gained naturally cools to room temperature, then controls rotating speed for 6000-
8000r/min is centrifuged, and the pH that the precipitate with deionized water of gained is washed to eluate is neutrality, then controls temperature
Dried for 40 DEG C -80 DEG C, obtained final product 26 face cuprous nano particles.
Present invention also offers the hexahedron cuprous nano particle of one kind 20 obtained by above-mentioned method is used as
Purposes in photochemical catalyst catalytic degradation organic pollution.
26 face cuprous nano particles of above-mentioned gained, exposed crystal face is relatively more, thus it can be used to be catalyzed
Degradable organic pollutant.When it is used for catalytic degradation organic pollution, the specific crystal face having due to it is to light-catalysed effect
Rate is higher, therefore can improve cuprous oxide as the catalytic efficiency of photochemical catalyst catalytic degradation organic pollution.
The hexahedron cuprous nano particle of one kind 20 of the present invention, because the specific crystal face having is to light-catalysed
Efficiency comparison is high, thus it improves cuprous oxide and drop as photochemical catalyst catalysis when being used for catalytic degradation organic pollution and reacting
The catalytic efficiency of solution organic pollution.The preparation method of the present invention, due to being prepared using hydro-thermal method, therefore with low production cost
Honest and clean, preparation process is simply controllable, is adapted to the characteristics of mass producing.
Description of the drawings
Fig. 1 is a kind of ESEM collection of illustrative plates of 20 hexahedron cuprous nano particle of the gained of embodiment 1.
Fig. 2 is a kind of wide-angle XRD of 20 hexahedron cuprous nano particle of the gained of embodiment 1.
Fig. 3 is a kind of degradation capability figure of the 20 hexahedron cuprous oxide of the gained of embodiment 1 to methyl orange.
Specific embodiment
Below by specific embodiment and combine accompanying drawing the invention will be further described, but the present invention be not limited to it is following
Embodiment.
Method described in various embodiments of the present invention if no special instructions, is conventional method.
It is raw materials used without special instruction in various embodiments of the present invention, can be commercially available from open commercial sources.
The model of instrument or equipment used by various embodiments of the present invention and the information of manufacturer are as follows：
Air dry oven, model DHG-9920A, manufacturer Shanghai one is permanent；
Xenon lamp, it is seen that sea blue bright Electronics Co., Ltd. on light source XQ350W；
X-ray diffraction (XRD), PANalytical company of X PERT PRO Holland；
Ultraviolet-uisible spectrophotometer, Shimadzu Corporation of UV-3600 Japan；
SEM (SEM), S-3400N HITs.
Embodiment 1
A kind of preparation method of 20 hexahedron cuprous nano particle, specifically includes following steps：
（1）, 0.02mol nitrate trihydrates copper dissolution obtained into copper nitrate solution in the solvent that 9ml deionized waters are constituted；
（2）, in step（1）0.1g ethylenediamines are added in the copper nitrate solution of gained, 10-20min is stirred, 0.1g hydrogen is added
Sodium oxide molybdena, is eventually adding 0.2g formic acid, and temperature is controlled after being uniformly mixed carries out reaction 2h at 50 DEG C；
（3）, step（3）After hydro-thermal reaction terminates, the reactant liquor of gained naturally cools to and control after room temperature centrifugal rotational speed and be
6000r/min is centrifuged, and the precipitate with deionized water of gained is washed to the pH of eluate and is to control temperature after neutrality
40-60 DEG C is dried, and obtains final product 20 hexahedron cuprous nano particles.
（4）, the catalyst of above-mentioned preparation carried out into photocatalytic degradation reaction, weigh 0.1g catalyst, add initial concentration
For the methyl orange solution 200mL of 25mg/L, 30min is stirred under dark room conditions, in making catalyst dispersion soln, and reach saturation
Absorption, timing sampling, centrifugation takes supernatant liquor and is analyzed with photometry.
By the cuprous nano particle of above-mentioned gained by scanning electron microscopic observation, as a result as shown in figure 1, can from Fig. 1
There are 26 faces with the cuprous nano particle obtained by finding out.
The cuprous nano particle of above-mentioned gained is characterized by X-ray diffraction (XRD), the wide-angle XRD of gained
As shown in Fig. 2 as can be seen from Figure 2 its relative intensity is higher, the degree of crystallinity for being indicated above sample is higher, and pattern is unconventional for figure
It is whole.
As can be seen from Figure 3 come, under the illumination condition of visible ray, will with the hexahedron cuprous oxide of 0.1g 20
200mL25mg/L degraded in 30 minutes and has reached more than 90%, showed that the cuprous oxide has strong catalysis activity to organic matter
Photocatalytic degradation.
Embodiment 2
A kind of 20 hexahedron cuprous nano particles, specifically include following steps：
（1）, by the deionized water of 0.34g nitrate trihydrate copper chlorinations copper dissolution 20 constitute solvent in copper chloride；
（2）, in step（1）0.5g hydrochloric acid is added in the copper chloride solution of gained, 10-20min is stirred, 0.1g hydrogen is added
Sodium oxide molybdena, is eventually adding 0.2g ascorbic acids, and 70 DEG C carry out reaction 4h after being uniformly mixed；
（3）, step（2）After hydro-thermal reaction terminates, the reactant liquor of gained naturally cools to and control after room temperature centrifugal rotational speed and be
7000r/min is centrifuged, and the precipitate with deionized water of gained is washed to the pH of eluate and is to control temperature after neutrality
60 DEG C are dried, and obtain final product cuprous nano particle.
Embodiment 3
A kind of preparation method of 20 hexahedron cuprous nano particle, specifically includes following steps：
（1）, by 0.45g nitrate trihydrates copper dissolution in the solvent that 27ml ethanol and 3ml deionized waters are constituted；
（2）, in step（1）Add in the copper nitrate solution of gained in 0.7g citric acids, stir 10-20min, add 0.3g
Ammoniacal liquor, adds reducing agent 0.2g ascorbic acid, and after being uniformly mixed, control temperature carries out reaction 6h at 90 DEG C；
（3）, step（2）After hydro-thermal reaction terminates, the reactant liquor of gained naturally cools to and control after room temperature centrifugal rotational speed and be
8000r/min is centrifuged, and the precipitate with deionized water of gained is washed to the pH of eluate and is to control temperature after neutrality
60-80 DEG C is dried, and obtains final product cuprous nano particle.
In sum, 20 hexahedron cuprous nano particles of the invention, expose more crystal faces, and it is used for light
Catalyst degradable organic pollutant is by with higher catalytic efficiency.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of without departing from the technology of the present invention principle, some improvement and modification can also be made, these improve and become
Type is regarded as protection scope of the present invention.
Claims (3)
1. a kind of preparation method of 20 hexahedron cuprous nano particle, it is characterised in that：
1）Inorganic mantoquita is dissolved in solvent and obtains inorganic copper salt solution；Described inorganic mantoquita be copper nitrate, copper sulphate or
Person's copper chloride；Described solvent is one kind of water, ethanol, methyl alcohol or ethylene glycol and the mixture of two or more compositions；
2）In step（1）Add additive in the inorganic copper salt solution of gained, described additive be hydrochloric acid, ethylenediamine or
The mixture of one kind of sodium citrate and two or more compositions；Stirring 10-20min, adds alkaline matter, described alkaline matter
The mixture of a kind of and two or more compositions for NaOH, potassium hydroxide, ammoniacal liquor or sodium acid carbonate, stirs 10-20min；
Add reducing agent, described reducing agent is that formic acid, acetaldehyde, glucose or ascorbic acid be a kind of and two or more compositions
Mixture, after being uniformly mixed, under the conditions of 30-90 DEG C, carries out reaction 0.5-6h；
3）Step（2）After reaction terminates, the reactant liquor of gained naturally cools to room temperature, then controls rotating speed for 6000-8000r/
Min is centrifuged, and the pH that the precipitate with deionized water of gained is washed to eluate is neutrality, and it is 40 then control temperature
DEG C -80 DEG C are dried, and obtain final product 26 face cuprous nano particles；
The material ratio of above-mentioned inorganic mantoquita used, solvent, additive, alkaline matter and reducing agent is 0.02mol：9ml：
0.1g:0.1g:0.2g；
Or, the material ratio of above-mentioned inorganic mantoquita used, solvent, additive, alkaline matter and reducing agent is 0.001mol：
20ml：0.5g:0.1g:0.2g；
Or, the material ratio of above-mentioned inorganic mantoquita used, solvent, additive, alkaline matter and reducing agent is 0.002mol：
30ml：0.7g:0.3g:0.2g.
2. a kind of preparation method of 20 hexahedron cuprous nano particle as claimed in claim 1, it is characterised in that：Institute
The inorganic mantoquita stated is copper nitrate, and described aqueous solvent, described additive is ethylenediamine, and described alkaline matter is bicarbonate
Sodium, described reducing agent is glucose.
3. the hexahedron cuprous nano particle of one kind 20 for being obtained by the method for claim 1 is used as photochemical catalyst catalysis
Purposes in degradable organic pollutant.
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| CN105923647B (en) * | 2016-04-14 | 2017-09-01 | 青岛大学 | A kind of preparation method of the brilliant assembly of cuprous nano |
| CN105836787B (en) * | 2016-05-23 | 2017-11-17 | 常州大学 | A kind of environment-friendly preparation method thereof of cuprous oxide |
| CN107915249B (en) * | 2016-10-08 | 2020-03-24 | 中国科学院大连化学物理研究所 | Nano Cu of square core-shell structure2O/Cu3Preparation method of N material |
| CN109704387B (en) * | 2019-01-17 | 2021-06-15 | 西安理工大学 | Icosahedron Cu2Preparation method of O mesoscopic crystal powder |
| CN110156064A (en) * | 2019-04-30 | 2019-08-23 | 南开大学 | A kind of low indices of crystallographic plane Cu2The preparation method of O Polyhedral Particles |
| CN111252800A (en) * | 2020-01-21 | 2020-06-09 | 上海电力大学 | Preparation method of nano cuprous oxide photoelectric material |
| CN112941643A (en) * | 2021-01-26 | 2021-06-11 | 南京捷纳思新材料有限公司 | Method for preparing photocatalytic fiber through microfluid electrostatic spinning |
| CN115259207B (en) * | 2022-08-30 | 2024-02-23 | 西北工业大学 | Preparation method of fourteen-surface cuprous oxide |
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| KR100797484B1 (en) * | 2006-08-29 | 2008-01-23 | 삼성전기주식회사 | Method for manufacturing cubic copper or copper oxide nanoparticles |
| CN101279759A (en) * | 2008-05-22 | 2008-10-08 | 上海第二工业大学 | Synthetic method of micron cuprous oxide in ultrasonic field |
| CN101773831A (en) * | 2009-11-27 | 2010-07-14 | 中国科学院广州地球化学研究所 | Micro-pore cuprous oxide visible light catalyst and preparation method and application thereof |
| CN103030169B (en) * | 2012-12-26 | 2015-07-15 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
| CN104803407B (en) * | 2015-04-15 | 2017-02-22 | 西安交通大学 | Preparation method of shape-controllable nano CuO (copper oxide) powder |
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