CN1208500C - Method for preparing nano copper protoxide material by metal copper anodic oxidation method - Google Patents
Method for preparing nano copper protoxide material by metal copper anodic oxidation method Download PDFInfo
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- CN1208500C CN1208500C CNB031187064A CN03118706A CN1208500C CN 1208500 C CN1208500 C CN 1208500C CN B031187064 A CNB031187064 A CN B031187064A CN 03118706 A CN03118706 A CN 03118706A CN 1208500 C CN1208500 C CN 1208500C
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Abstract
A copper anode is used for dissolving in a chloride medium, which is a mature flow for producing cuprous oxide (Cu2O), but the flow is only used for producing powder with a micrometer particle diameter. A growth inhibitor of Cu2O crystallization or/and a Cu2O crystallization centre, or a carrier containing a crystallization centre, or/and other nanometer materials are added in a chloride electrolyte; in electrolytic solution, the concentration of chloride salt, alkaline concentration, the electric quantity of electric energy and electrolytic temperature are controlled; therefore, Cu2O powder of which the particle diameter is less than 100 nm, nanometer Cu2O with a carrier, or nanometer composite materials, such as Cu2O carbon nanometer tubes and Cu2O nanometer titanium dioxide, can be obtained.
Description
Technical Field
The present invention belongs to a method for preparing nano cuprous oxide with photocatalysis function
Background
Cuprous oxide (Cu)2O) is a visible light catalyst, can be widely applied to solar cells, wastewater treatment, gas purification, sterilization, deodorization, pesticides, ship antifouling paint and the like, and is also a catalyst commonly used in the petrochemical industry. As the photocatalyst, there are advantages in that visible light in sunlight can be utilized, and there is a disadvantage in that recombination rate of generated electrons and holes is high, thus being higher than that of titanium dioxide (TiO)2) The utilization rate of light energy is low. To overcome the disadvantage of low efficiency, the surface area of the photocatalyst must be increased, one of the ways is to add Cu2O is deposited on glass fibers or porous materials (appl. surf. Sci.174: 177 (2001); J. Elecrochem. Soc.147 (2): 486(2000)), and its most thorough method should be to prepare nano-Cu2And (3) O material.
So far, no commercial nano Cu exists2O appears, and the preparation of nano Cu is not found2O. Preparation of nano Cu published in various periodicals2The physical methods of O are: plasma evaporation (Thin solid films.213: 226 (1992); appl. Phys. Lett.79: 3176(2001)), microwave irradiation (chemical world. 2000, 12: 632), chemical vapor deposition (Sol. Mater. Sol.cell.5: 85 (1998); adv.Mater.7: 562(1995)), gamma-ray irradiation (Mater. Res. Bull.29: 277(1994)), ultraviolet irradiation (Medit. 33: 330 (1997)). However, these physical methods are mostly costly or not easily industrialized. The mechanical milling methods commonly used for the preparation of nanomaterials have not been successful because monovalent copper ions are catalytically oxidized to divalent copper ions by mechanical forces during the ball milling process (mater.sci.forum.1999: 312). The sol-gel method which is also commonly used only produces Cu2Report on O colloidal solution (scientific report: 38: 1609 (1993); Angew. chem. int. Ed. 40: 359(2001)), Cu in wet state2O is highly susceptible to oxidation during the separation process. Reduction of copper salts with glucose by covering with polyvinylpyrrolidone (PVP)By using the method, 10-50nm Cu can be prepared2O(J.Colloid Int.Sci.214:95(1973))。
Electrochemical method for preparing nano Cu2O is possible. Anodic oxidation of Cu onto the surface of a copper electrode2The O thin layer method has been widely reported for solar cell research. A thin 15nm layer (Phys. chem.103: 395(1999)) was obtained with appropriate control of the conditions, but the Cu formed2Most of O is reduced into metallic copper under the action of photocathode, and nano Cu can not be prepared2And (3) O powder. When using formonitrile and tetrahydrofuran as solvent,When the stabilizer is added, the metal copper is dissolved at the anode to obtain 2nm Cu2O (J.Am.chem.Soc., 116: 7401 (1994)). However, this method requires slow electrolysis, resulting in a slow production rate. The process of anodic dissolution of copper in chloride salt medium to produce cuprous oxide is industrialized, the method is low in cost, mature and the product Cu2O has stable quality and the process is easy to control (J.Appl.electrochen.20: 826(1990)), but the obtained Cu2The diameter of O is several microns.
Disclosure of Invention
The invention aims to utilize the economical, mature and easily controlled anode dissolution process in chloride salt medium to produce Cu2Preparation of nano Cu by virtue of O stability2And (3) O material.
The principle of the invention is as follows: in the chloride salt (MeCl, Me ═ Na)+,K+,Li+,NH4 +R4N +, etc.), anodic dissolution of the copper anode during electrolysis can occur.
When the solution contains alkali, hydrolysis reaction occurs to generate Cu2O;
Generally, newly formed Cu2And the O continues to grow at the previously formed crystal center, so that the crystal grows up and finally micron-sized powder is formed. For the inventionThree methods for Cu suppression2Particle size of O: (1) adding Cu to the electrolyte facing the copper anode2A crystal growth inhibitor of O; the growth inhibitor can be polyvinyl alcohol, PVP and its derivatives, or copper surface adsorbent such as octyl ammonium bromide, benzotriazole, etc. (2) Adding a large amount of Cu into the electrolyte2Nucleation centers of O or carriers containing nucleation centers. (3) Adding another nano material as Cu into the electrolyte2A carrier of O. These three methods may be used alone or in combination. Cu thus obtained2The amount of O particles is large and the granularity is small, and the nano Cu can be obtained by controlling the electrolytic current density and the electrolytic electric quantity and stopping electrolysis when the O particles grow to tens of nanometers2And O. Then proper washing, stabilization and vacuum drying are carried out to finally obtain the stable nano Cu which can be stored for a long time2O。
The scheme for realizing the purpose of the invention is as follows: preparation of nano cuprous oxide (Cu) by metal copper anodic oxidation method2O) material, by anodic dissolution electrolysis of metallic copper anodes in chloride salt solutions, adding Cu to the electrolyte facing the copper anodes2O crystal growth inhibitor, or/and crystal center, or carrier containing crystal center, or/and another nano material, and controlling chloride salt concentration in electrolyte, alkali concentration, electrolyte temperature, and electrolytic capacity to obtain Cu with particle size less than 100nm2O powder or nano Cu containing carrier2O, or a nanocomposite.
Cu as described above2The crystal growth inhibitor of O is polyvinyl alcohol, polyvinylpyrrolidone and derivatives thereof,Octyl ammonium bromide, benzotriazole.
The concentration of the chloride salt MeCl solution in the electrolyte is 0.01-4.0M. Preferably 0.1 to 3.5M.
The concentration of the alkali contained in the electrolyte is generally 10-8 to 3.0M. Preferably 10-6-10-1M
The electrolysis is carried out at a temperature of generally 30 to 90 ℃. The preferred temperature range is 60-90 ℃.
The current density of the anode used in the above electrolysis is oneGenerally 0.005-5A/dm3. Preferably 0.1-2A/dm2。
The electrolytic capacity of the electrolysis per liter of the electrolyte is controlled to be below 20 ampere-hour. Preferably<5 A.h
Adding Cu into the electrolyte2The carbon nano tube carrier of the O crystal center is used for obtaining the nano Cu2An O-carbon nanotube composite.
Adding another nano material of titanium dioxide (TiO) into the electrolyte2) Can produce Cu2O-TiO2A nanocomposite material.
Detailed Description
Example 1: using 1dm2The copper plate is used as an anode, titanium or nickel is used as a cathode, and a diaphragm is arranged between the cathode and the anode to prevent hydrogen bubbles generated by the cathode from contacting with generated Cu2And O. 3.5MNaCl-0.01MNaOH is placed in the electrolytic bath as electrolyte. Suspending 1g of carbon nanotubes supported on monovalent copper crystal centers at 80 ℃ and 0.5A/dm2Electrolyzing for 60 minutes under the electrolysis condition of current density. After the electrolysis is finished, taking out the carbon-containing nano tube-Cu2And removing the electrolyte by centrifugal separation or filtration, washing, stabilizing and vacuum-drying the precipitate.
Cu obtained by observation with a transmission electron microscope2O-carbon nanotube composite, finding Cu2O is in the form of dark granular particles grown on carbon nanotubes in light grey. Cu2The particle size of O is between 20 and 80 nm. Cu2The O particles are attached to the carbon nanotubes substantially in a monolayer and X-diffraction shows Cu2The characteristic of O crystal. Cu2The weight ratio of O to the carbon nano tube is as high as 1.5: 1.
Example 2: 0.001M benzotriazole was added to the chloride solution in the electrolytic cell described in example one, the amount of electrolytic electricity was controlled to 5 A.h/L, the electrolytic solution was vigorously stirred during the electrolysis, washed, dried, and observed with a microscope to give an octahedral Cu product2O crystal with an average particle diameter of 60 to 80 nm.
Example 3: by vapour deposition on commercial graphite powderIntroducing trace copper element, suspending graphite powder containing copper crystal centers in the electrolyte shown in the first embodiment, electrolyzing, washing and drying under the conditions of the first embodiment to obtain Cu2O-activated carbon composite, Cu shown by electron microscope observation2O is attached to the active particles in the size of 10-80nmOn charcoal.
Example 4: in the chloride solution of the electrolytic cell described in example one, 1g of nano TiO was suspended2(P25, Degussa, Germany), electrolyzed, washed and dried under the same conditions. Electron microscope observation and X-diffraction prove that the product is Cu2O-TiO2A composite nano photocatalyst.
Claims (4)
1. A process for preparing the nano cuprous oxide material by anodic oxidation of metallic copper features that the metallic copper anode is dissolved in the solution of chloride salt for electrolysis, and Cu is added to the electrolyte opposite to said metallic copper anode2O crystal growth inhibitor, or/and crystal center, or carrier containing crystal center, or/and another nanometer material, and controlling the concentration of chloride salt in electrolyte to 0.01-4.0M and the concentration of alkali to 10-8-3.0M, 30-90 deg.C, 20 A.h or less, and 0.005-5A/dm of anode current density3To obtain Cu with grain size less than 100nm2O powder or nano Cu containing carrier2O, or a nanocomposite.
2. The method of claim 1, wherein said Cu is2The crystal growth inhibitor of O is polyvinyl alcohol, polyvinylpyrrolidone and derivatives thereof, octyl ammonium bromide and benzotriazole.
3. The method as set forth in claim 1, wherein Cu is added to the electrolyte2The carbon nano tube carrier of the O crystal center is used for obtaining the nano Cu2An O-carbon nanotube composite.
4. The method of claim 1The method is characterized in that another nano material titanium dioxide is added into the electrolyte to prepare Cu2O-TiO2A nanocomposite material.
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Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100389230C (en) * | 2005-12-20 | 2008-05-21 | 厦门大学 | Process for preparing shape controllable cuprous oxide micro/nano crystal by electrochemical deposition |
CN101956223B (en) * | 2010-10-27 | 2012-11-14 | 厦门大学 | Method for preparing cuprous oxide composite titanium dioxide nanotube array |
CN102978678A (en) * | 2012-10-30 | 2013-03-20 | 上海交通大学 | Preparation method for cuprous chloride film through anodic oxidation |
CN102965711B (en) * | 2012-11-06 | 2016-01-13 | 上海交通大学 | The anodic oxidation two-step preparation method of cuprous nano flaky powder material |
CN103014815B (en) * | 2012-11-28 | 2016-05-04 | 常州大学 | Copper conductor roll-type fast anode oxidation treatment method |
CN105483743A (en) * | 2014-09-16 | 2016-04-13 | 江苏泰禾金属工业有限公司 | Device and method for preparing cuprous oxide through electrolysis |
CN104402037B (en) * | 2014-10-24 | 2016-05-18 | 福建工程学院 | A kind of method of preparing nano cuprous oxide from printed substrate copper-contained sludge |
CN106591922B (en) * | 2017-02-05 | 2018-05-08 | 桂林理工大学 | Cu2Preparation method of O nano film |
CN107630227A (en) * | 2017-08-04 | 2018-01-26 | 天津理工大学 | A kind of method that three-D nano-porous copper mesh elctro-catalyst is prepared based on metal net |
CN109811364B (en) * | 2019-01-10 | 2020-10-27 | 北京化工大学 | Ruthenium/cuprous oxide electro-catalytic material and preparation method thereof |
CN114232003B (en) * | 2021-12-16 | 2023-09-12 | 西北师范大学 | Cu preparation by utilizing cathode glow discharge electrolysis plasma technology 2 Method of O nanoparticles |
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