WO2013174250A1 - Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor - Google Patents

Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor Download PDF

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Publication number
WO2013174250A1
WO2013174250A1 PCT/CN2013/075970 CN2013075970W WO2013174250A1 WO 2013174250 A1 WO2013174250 A1 WO 2013174250A1 CN 2013075970 W CN2013075970 W CN 2013075970W WO 2013174250 A1 WO2013174250 A1 WO 2013174250A1
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copper oxide
coated
copper
oxide
preparing
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PCT/CN2013/075970
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French (fr)
Chinese (zh)
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覃东棉
刘华胜
朱刘
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广东先导稀材股份有限公司
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Publication of WO2013174250A1 publication Critical patent/WO2013174250A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other

Definitions

  • the invention relates to a synthetic material and a preparation method thereof, in particular to a composite material of copper oxide surface coated with copper oxide and a preparation method thereof. Background technique
  • the antifouling coating is mainly composed of a resin, an antifouling agent, a pigment filler, and an auxiliary agent, and an antifouling agent plays a decisive role.
  • Cuprous oxide is one of the oldest antifouling agents in use, and it has the advantages of safety and low cost.
  • the second is that the release rate of copper ions in seawater is faster (5.4 g/ Ml), the life expectancy of cuprous oxide antifouling paint is short.
  • U.S. Patent No. 5,707,438 discloses a method of oxidizing a copper oxide protective layer on the surface of cuprous oxide by a pyrometallurgical method to prevent the continued oxidation of cuprous oxide in the air and to control the oxidation of the cuprous oxide.
  • the rate of dissolution of copper in seawater due to the method of fire used in this patent, can cause oxidative inhomogeneities and uncontrollable thickness of the oxide layer.
  • Another object of the present invention is to provide a composite material of copper oxide surface coated with copper oxide and a preparation method thereof, which can realize controllable thickness of the coated copper oxide.
  • the present invention provides a method for preparing a composite material of copper oxide surface-coated copper oxide, comprising the steps of: dispersing a cuprous oxide powder in a fraction
  • the liquid and sodium hydroxide solution are added to the suspension to carry out the coating reaction, and the pH is maintained during the coating reaction.
  • the value is unchanged to form a reaction product, and the reaction product is coated with copper oxide on the surface of cuprous oxide.
  • the present invention provides a method for preparing a copper oxide surface-coated copper oxide composite material comprising the steps of: dispersing a cuprous oxide powder in a deionized water containing a dispersant; To prepare a suspension; at a predetermined temperature and a predetermined pH value, a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction.
  • the product is a composite material in which copper oxide is coated with copper oxide on the surface of the cuprous oxide; after the coating reaction, it is cooled to room temperature; and the reaction product is filtered, washed, and dried.
  • the present invention provides a composite material of copper oxide surface-coated copper oxide, which is coated with copper oxide on the surface of cuprous oxide according to the first invention of the present invention.
  • the preparation method of the material is prepared.
  • a layer of copper oxide is oxidized on the surface of the cuprous oxide.
  • the present invention employs a solution reaction method for surface coating to obtain a relatively uniform copper oxide coating layer.
  • a layer of copper oxide is oxidized on the surface of cuprous oxide.
  • the present invention adopts a solution reaction method for surface coating, and the thickness of the coating layer can be based on the coating agent. The amount of addition to control.
  • the composite material of the cuprous oxide surface coated with copper oxide obtained by the invention can prevent the conversion of cuprous oxide into copper oxide in air on the one hand, thereby losing the antifouling function; on the other hand, the cuprous oxide can be controlled The rate of release in seawater, the waste of cuprous oxide and its contamination of the water environment by the deposition of offshore and port terminals.
  • a method for preparing a composite material of copper oxide surface coated with copper oxide comprising the steps of: dispersing a cuprous oxide powder in deionized water containing a dispersing agent to prepare a suspension; at a predetermined temperature, a prescribed pH The copper salt solution and the sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction product, and the reaction product is a cuprous oxide surface.
  • the particle size of the cuprous oxide powder is 50 ⁇ ! ⁇ 10 ⁇ m; cuprous oxide concentration is 50g / L ⁇ 500g / L o
  • the dispersing agent is selected from sodium dodecylbenzenesulfonate, sodium dodecyl sulfate or sodium heptaacetate or a mixture of them. 5 g/L ⁇ More preferably, the concentration of the dispersing agent is 0. 05 g / L ⁇ 0. 5 g / L.
  • the predetermined temperature range is from 70 ° C to 90 ° C
  • the pH range is from 8 to 10
  • the coating reaction is carried out.
  • the time is 0. 5 ⁇ 2h.
  • the copper salt solution is a copper sulfate solution. More preferably, the concentration of the copper sulfate solution is concentrated The degree is from 10 g/L to 100 g/L, and the amount of copper sulfate contained in the copper sulfate solution is 5% to 25% of the mass of the cuprous oxide powder.
  • the concentration of the sodium hydroxide solution is from 4 g / L to 16 g / L.
  • the thickness of the copper oxide coated on the surface of the cuprous oxide is 5 nm to 50 nm.
  • a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a magnetic stirring during the coating reaction.
  • the rate of magnetic stirring is 200 to 500 rpm.
  • the temperature at the time of drying is 50 °C.
  • Step 1 Add 100 ml of deionized water to a round bottom flask, add 0. 005 g of sodium dodecylbenzene sulfonate, stir and dissolve, add 5 g of 50 nm cuprous oxide powder, and ultrasonically disperse for 15 min to obtain stable dispersion. Cuprous oxide suspension;
  • the sodium hydroxide solution was slowly added dropwise to the suspension, and the pH was kept constant during the coating reaction.
  • the coating reaction time was 0.5 h, stirring was continued until cooling to room temperature, then filtered and washed at 50 ⁇ . Drying is performed to obtain a copper oxide-coated cuprous oxide powder.
  • the first step is to add 100ml of deionized water to the round bottom flask, and add 0. 05g Sodium sulphate, stirred and dissolved, then added 27. 5 g of 500 nm cuprous oxide powder, ultrasonic dispersion for 15 min to obtain a stable dispersion of cuprous oxide suspension;
  • Step 2 Transfer the above suspension to a magnetic stirrer, heat the suspension to 80 °C at 350 rpm, adjust the pH to 9, and use a peristaltic pump to apply 75 g/L of copper sulfate solution 75 ml and 12 g. /L sodium hydroxide solution is slowly added dropwise to the suspension, the pH value remains unchanged during the coating reaction, the coating reaction time is lh, stirring is continued until cooling to room temperature, then filtered and washed at 50 ° C Drying, copper oxide coated cuprous oxide powder is obtained. .
  • First step Add 100ml of deionized water to the round bottom flask, add 0. 0275g sodium hexametaphosphate, stir and dissolve, add 50g l 0m of cuprous oxide powder, and ultrasonically disperse for 15min to obtain stable dispersed oxide oxide. Copper suspension;
  • Step 2 Transfer the above suspension to a magnetic stirrer, heat the suspension to 90 °C at 500 rpm, adjust the pH to 10, and use a peristaltic pump to apply 125 g and 16 g of 100 g/L copper sulfate solution. /L sodium hydroxide solution was slowly added dropwise to the suspension, the pH value was kept constant during the coating reaction, the coating reaction time was 2 h, stirring was continued until cooling to room temperature, then filtered and washed with water and dried at 50 Torr. Dry, copper oxide coated cuprous oxide powder is obtained.
  • the detection result of Examples 1-3 was a focused beam ion technique.
  • the thickness of the copper oxide coated on the cuprous oxide powder was 5 nm in Example 1, 25 nm in Example 2, and 50 nm in Example 3.
  • the copper oxide-coated composite material of the cuprous oxide surface according to the present invention is obtained in accordance with the aforementioned preparation method.
  • the particle size of the cuprous oxide powder is 50 ⁇ ! ⁇ 10 ⁇ m
  • cuprous oxide coated with copper oxide Thickness is 5nm ⁇ 50nm c

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Disclosed are a composite of cuprous oxide surface-coated with copper oxide and the preparation method therefor, the preparation comprising the steps of: dispersing a cuprous oxide powder into deionized water containing a dispersant to prepare a suspension; adding a copper salt solution and a sodium hydroxide solution into the suspension to perform a coating reaction at a specified temperature and a specified pH value, during the coating reaction, the pH value being kept constant to form a resultant of the reaction, the resultant of the reaction being a composite of cuprous oxide surface-coated with copper oxide; cooling to room temperature after the coating reaction; filtering, washing, and drying the resultant of the reaction. The composite is prepared by the preparation method. A uniform copper oxide coating layer can be obtained. The thickness of the coating layer can be controlled.

Description

氧化亚铜表面包覆氧化铜的复合材料及其制备方法 技术领域  Composite material coated with copper oxide on copper oxide surface and preparation method thereof
本发明涉及一种合成材料及其制备方法， 尤其涉及一种氧化亚铜表面包 覆氧化铜的复合材料及其制备方法。 背景技术  The invention relates to a synthetic material and a preparation method thereof, in particular to a composite material of copper oxide surface coated with copper oxide and a preparation method thereof. Background technique
广袤的海洋为人类带来了丰富的自然资源， 然而在人类开发海洋资源的 过程中遇到了生物污损的重大难题， 海洋污损生物附着在船只、 海上钻井平 台、 浮标、 海上养殖设施、 海洋探测仪器等各种水上设施上， 会导致船舶重 量的增加， 使船底面更加的粗糙， 从而产生船舶航行时的阻力， 消耗更多的 燃料， 损害动力机械， 缩短坞修时间间隔以及缩短船舶的使用寿命， 从而带 来巨大的经济损失。 迄今为止， 防止海洋生物污损行之有效和普遍采用的方 法是涂刷防污涂料。防污涂料主要由树脂、防污剂、颜填料和助剂等所组成， 其中起决定作用的是防污剂。 氧化亚铜是使用历史最悠久的防污剂之一， 具 有安全、 价廉等优点。 但氧化亚铜用于防污涂料还存在一定局限性， 其一是 氧化亚铜在空气中不稳定， 容易被氧化； 其二是铜离子在海水中的释放速率 较快 （5. 4 g/ml ) ， 氧化亚铜防污漆的使用寿命较短。  The vast ocean brings abundant natural resources to human beings. However, in the process of human development of marine resources, it encounters major problems of biofouling. Marine fouling organisms are attached to ships, offshore drilling platforms, buoys, marine breeding facilities, and oceans. Various water facilities such as detection instruments will cause the weight of the ship to increase, making the bottom of the ship more rough, resulting in the resistance of the ship during navigation, consuming more fuel, damaging the power machinery, shortening the docking time interval and shortening the ship's The service life, resulting in huge economic losses. To date, effective and widespread methods for preventing marine biofouling have been to apply antifouling coatings. The antifouling coating is mainly composed of a resin, an antifouling agent, a pigment filler, and an auxiliary agent, and an antifouling agent plays a decisive role. Cuprous oxide is one of the oldest antifouling agents in use, and it has the advantages of safety and low cost. However, there are some limitations in the use of cuprous oxide in antifouling coatings. One is that cuprous oxide is unstable in air and is easily oxidized. The second is that the release rate of copper ions in seawater is faster (5.4 g/ Ml), the life expectancy of cuprous oxide antifouling paint is short.
为改善氧化亚铜的这些缺点， 美国专利 US5707438提出了一种采用火法 的方法在氧化亚铜的表面氧化出氧化铜保护层， 从而防止氧化亚铜在空气中 的继续氧化并控制了氧化亚铜在海水中的溶解速度， 由于该专利使用的火法 的方法， 会造成氧化的不均性以及氧化层厚度的不可控性。 发明内容  In order to improve these disadvantages of cuprous oxide, U.S. Patent No. 5,707,438 discloses a method of oxidizing a copper oxide protective layer on the surface of cuprous oxide by a pyrometallurgical method to prevent the continued oxidation of cuprous oxide in the air and to control the oxidation of the cuprous oxide. The rate of dissolution of copper in seawater, due to the method of fire used in this patent, can cause oxidative inhomogeneities and uncontrollable thickness of the oxide layer. Summary of the invention
鉴于现有技术存在的问题， 本发明的目的在于提供一种氧化亚铜表 面包覆氧化铜的复合材料及其制备方法， 其能实现所包覆的氧化铜的厚 度均匀。  In view of the problems of the prior art, it is an object of the present invention to provide a composite material of copper oxide surface coated with copper oxide and a preparation method thereof, which can achieve uniform thickness of the coated copper oxide.
本发明的另一目的在于提供一种氧化亚铜表面包覆氧化铜的复合材 料及其制备方法， 其能实现所包覆的氧化铜的厚度可控。 为了实现本发明的上述目的， 在第一方面， 本发明提供一种氧化亚 铜表面包覆氧化铜的复合材料的制备方法包括步骤： 将氧化亚铜粉体分 散在含分 Another object of the present invention is to provide a composite material of copper oxide surface coated with copper oxide and a preparation method thereof, which can realize controllable thickness of the coated copper oxide. In order to achieve the above object of the present invention, in a first aspect, the present invention provides a method for preparing a composite material of copper oxide surface-coated copper oxide, comprising the steps of: dispersing a cuprous oxide powder in a fraction
散剂的去离子水中， 以制备悬浊液； 在规定温度、 规定 pH值下， 将 铜盐溶  Dissolve the deionized water to prepare a suspension; dissolve the copper salt at a specified temperature and a specified pH.
液、 氢氧化钠溶液加入到悬浊液中进行包覆反应， 包覆反应过程中 保持 pH  The liquid and sodium hydroxide solution are added to the suspension to carry out the coating reaction, and the pH is maintained during the coating reaction.
值不变， 以形成反应生成物， 所述反应生成物为氧化亚铜表面包覆 氧化铜的  The value is unchanged to form a reaction product, and the reaction product is coated with copper oxide on the surface of cuprous oxide.
为了实现本发明的上述目的， 在第一方面， 本发明提供一种氧化亚 铜表面包覆氧化铜的复合材料的制备方法包括步骤： 将氧化亚铜粉体分 散在含分散剂的去离子水中， 以制备悬浊液；在规定温度、规定 pH值下， 将铜盐溶液、 氢氧化钠溶液加入到悬浊液中进行包覆反应， 包覆反应过 程中保持 pH值不变， 以形成反应生成物， 所述反应生成物为氧化亚铜表 面包覆氧化铜的复合材料； 包覆反应之后， 冷却至室温； 对反应生成物 进行过滤、 洗涤、 干燥。  In order to achieve the above object of the present invention, in a first aspect, the present invention provides a method for preparing a copper oxide surface-coated copper oxide composite material comprising the steps of: dispersing a cuprous oxide powder in a deionized water containing a dispersant; To prepare a suspension; at a predetermined temperature and a predetermined pH value, a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction. The product is a composite material in which copper oxide is coated with copper oxide on the surface of the cuprous oxide; after the coating reaction, it is cooled to room temperature; and the reaction product is filtered, washed, and dried.
为了实现本发明的上述目的， 在第二方面， 本发明提供一种氧化亚 铜表面包覆氧化铜的复合材料 ，其依据本发明第一发明所述的氧化亚铜 表面包覆氧化铜的复合材料的制备方法制备。  In order to achieve the above object of the present invention, in a second aspect, the present invention provides a composite material of copper oxide surface-coated copper oxide, which is coated with copper oxide on the surface of cuprous oxide according to the first invention of the present invention. The preparation method of the material is prepared.
本发明的有益效果如下。  The beneficial effects of the present invention are as follows.
相比于现有的采用火法的方法在氧化亚铜表面氧化出一层氧化铜， 本发明采用的是溶液反应法进行表面包覆， 可获得较为均匀的氧化铜包 覆层。  Compared with the prior art method using a fire method, a layer of copper oxide is oxidized on the surface of the cuprous oxide. The present invention employs a solution reaction method for surface coating to obtain a relatively uniform copper oxide coating layer.
相比于现有的采用火法的方法在氧化亚铜表面氧化出一层氧化铜， 本发明采用的是溶液反应法进行表面包覆， 包覆层的厚度可根据包覆剂 的添加量来控制。 Compared with the existing method using fire method, a layer of copper oxide is oxidized on the surface of cuprous oxide. The present invention adopts a solution reaction method for surface coating, and the thickness of the coating layer can be based on the coating agent. The amount of addition to control.
通过本发明获得的氧化亚铜表面包覆氧化铜的复合材料， 在使用时 一方面可以防止氧化亚铜在空气中转变成氧化铜， 从而丧失防污功能； 另一方面可以控制氧化亚铜在海水中的释放速率， 较少氧化亚铜的浪费 以及其对近海、 港口码头的沉积对水环境的污染。 具体实 式  The composite material of the cuprous oxide surface coated with copper oxide obtained by the invention can prevent the conversion of cuprous oxide into copper oxide in air on the one hand, thereby losing the antifouling function; on the other hand, the cuprous oxide can be controlled The rate of release in seawater, the waste of cuprous oxide and its contamination of the water environment by the deposition of offshore and port terminals. Specific form
下面首先说明根据本发明的氧化亚铜表面包覆氧化铜的复合材料的 制备方法。  Next, a method of preparing a composite material of copper oxide surface-coated copper oxide according to the present invention will be described first.
根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法， 包 括步骤： 将氧化亚铜粉体分散在含分散剂的去离子水中， 以制备悬浊液; 在规定温度、 规定 pH值下， 将铜盐溶液、 氢氧化钠溶液加入到悬浊液中 进行包覆反应， 包覆反应过程中保持 pH值不变， 以形成反应生成物， 所 述反应生成物为氧化亚铜表面包覆氧化铜的复合材料； 包覆反应之后， 冷却至室温； 对反应生成物进行过滤、 洗涤、 干燥。 在根据本发明的氧 化亚铜表面包覆氧化铜的复合材料的制备方法中， 优选地， 在制备悬浊 液时， 氧化亚铜粉体的粒度为 50ηπ！〜 10 μ m; 氧化亚铜的浓度为 50g/L〜 500g/L o  A method for preparing a composite material of copper oxide surface coated with copper oxide according to the present invention, comprising the steps of: dispersing a cuprous oxide powder in deionized water containing a dispersing agent to prepare a suspension; at a predetermined temperature, a prescribed pH The copper salt solution and the sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH is kept constant during the coating reaction to form a reaction product, and the reaction product is a cuprous oxide surface. A composite material coated with copper oxide; after the coating reaction, it is cooled to room temperature; the reaction product is filtered, washed, and dried. In the method for producing a composite material of copper oxide coated with copper oxide according to the present invention, preferably, in the preparation of the suspension, the particle size of the cuprous oxide powder is 50 ηπ! ~ 10 μ m; cuprous oxide concentration is 50g / L ~ 500g / L o
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 分散剂选自十二烷基苯磺酸钠、 十二垸基硫酸钠或六偏磔 酸钠或它们的混合物。 更优选地， 分散剂的浓度为 0. 05 g/L〜0. 5 g/L。  In the method for preparing a copper oxide-coated composite material according to the present invention, preferably, the dispersing agent is selected from sodium dodecylbenzenesulfonate, sodium dodecyl sulfate or sodium heptaacetate or a mixture of them. 5 g/L。 More preferably, the concentration of the dispersing agent is 0. 05 g / L ~ 0. 5 g / L.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 所述规定温度范围为 70 °C〜90 °C， pH值范围为 8〜10， 包 覆反应的时间为 0. 5〜2h。  In the method for preparing a copper oxide-coated composite material according to the present invention, preferably, the predetermined temperature range is from 70 ° C to 90 ° C, and the pH range is from 8 to 10, and the coating reaction is carried out. The time is 0. 5~2h.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 所述铜盐溶液为硫酸铜溶液。 更优选地， 硫酸铜溶液的浓 度为 10g/L〜100g/L，硫酸铜溶液中所含的硫酸铜的量为氧化亚铜粉体质 量的 5%〜25%。 优选地， 氢氧化钠溶液的浓度为 4g/L〜16g/L。 In the method for producing a copper oxide-coated composite material according to the present invention, preferably, the copper salt solution is a copper sulfate solution. More preferably, the concentration of the copper sulfate solution is concentrated The degree is from 10 g/L to 100 g/L, and the amount of copper sulfate contained in the copper sulfate solution is 5% to 25% of the mass of the cuprous oxide powder. Preferably, the concentration of the sodium hydroxide solution is from 4 g / L to 16 g / L.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 在所述复合材料中， 氧化亚铜表面包覆的氧化铜的厚度为 5nm〜50nm。  In the method for producing a copper oxide-coated composite material according to the present invention, preferably, in the composite material, the thickness of the copper oxide coated on the surface of the cuprous oxide is 5 nm to 50 nm.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法， 优选地， 在制备悬浊液时采用超声分散。  In the preparation method of the copper oxide-coated composite material according to the present invention, it is preferred to employ ultrasonic dispersion in the preparation of the suspension.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 在将铜盐溶液、 氢氧化钠溶液加入到悬浊液中进行包覆反 应过程中加有磁力搅拌。 更优选地， 磁力搅拌的速率为 200〜500rpm。  In the method for preparing a copper oxide-coated composite material according to the present invention, preferably, a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a magnetic stirring during the coating reaction. . More preferably, the rate of magnetic stirring is 200 to 500 rpm.
在根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备方法 中， 优选地， 干燥时的温度为 50 °C。  In the method for producing a copper oxide-coated composite material according to the present invention, preferably, the temperature at the time of drying is 50 °C.
其次说明根据本发明的氧化亚铜表面包覆氧化铜的复合材料的制备 方法的实施例。  Next, an embodiment of a method of preparing a copper oxide-coated composite material of cuprous oxide according to the present invention will be described.
实施例 1  Example 1
第一步： 在圆底烧瓶中加入 100ml 的去离子水， 加入 0. 005g 十二 垸基苯磺酸钠，搅拌溶解后加入 5g 50nm的氧化亚铜粉体，超声分散 15min 制得稳定分散的氧化亚铜悬浊液；  Step 1: Add 100 ml of deionized water to a round bottom flask, add 0. 005 g of sodium dodecylbenzene sulfonate, stir and dissolve, add 5 g of 50 nm cuprous oxide powder, and ultrasonically disperse for 15 min to obtain stable dispersion. Cuprous oxide suspension;
第二歩： 将上述悬浊液移至磁力搅拌器中， 200rpm条件下将悬浊液 加热至 70 °C， 把 pH 值调节至 8， 用蠕动泵把 10g/L 的硫酸铜溶液 25ml 和 4g/L的氢氧化钠溶液缓慢滴加到悬浊液中，包覆反应过程中保持 pH值 不变， 包覆反应时间为 0. 5h， 继续搅拌直至冷却至室温， 然后过滤水洗 并在 50 Ό下烘干， 制得氧化铜包覆的氧化亚铜粉体。  Second: Transfer the above suspension to a magnetic stirrer, heat the suspension to 70 °C at 200 rpm, adjust the pH to 8, and use a peristaltic pump to apply 25 ml and 4 g of 10 g/L copper sulfate solution. The sodium hydroxide solution was slowly added dropwise to the suspension, and the pH was kept constant during the coating reaction. The coating reaction time was 0.5 h, stirring was continued until cooling to room temperature, then filtered and washed at 50 Ό. Drying is performed to obtain a copper oxide-coated cuprous oxide powder.
实施例 2  Example 2
第一步： 在圆底烧瓶中加入 100ml 的去离子水， 加入 0. 05g十二垸 基硫酸钠， 搅拌溶解后加入 27. 5g 500nm氧化亚铜粉体， 超声分散 15min 制得稳定分散的氧化亚铜悬浊液； The first step is to add 100ml of deionized water to the round bottom flask, and add 0. 05g Sodium sulphate, stirred and dissolved, then added 27. 5 g of 500 nm cuprous oxide powder, ultrasonic dispersion for 15 min to obtain a stable dispersion of cuprous oxide suspension;
第二步： 将上述悬浊液移至磁力搅拌器中， 350rpm条件下将悬浊液 加热至 80 °C， 把 pH 值调节至 9， 用蠕动泵把 55g/L 的硫酸铜溶液 75ml 和 12g/L的氢氧化钠溶液缓慢滴加到悬浊液中， 包覆反应过程中保持 pH 值不变， 包覆反应时间为 lh， 继续搅拌直至冷却至室温， 然后过滤水洗 并在 50 °C下烘干， 制得氧化铜包覆的氧化亚铜粉体。 。  Step 2: Transfer the above suspension to a magnetic stirrer, heat the suspension to 80 °C at 350 rpm, adjust the pH to 9, and use a peristaltic pump to apply 75 g/L of copper sulfate solution 75 ml and 12 g. /L sodium hydroxide solution is slowly added dropwise to the suspension, the pH value remains unchanged during the coating reaction, the coating reaction time is lh, stirring is continued until cooling to room temperature, then filtered and washed at 50 ° C Drying, copper oxide coated cuprous oxide powder is obtained. .
实施例 3  Example 3
第一步： 在圆底烧瓶中加入 100ml 的去离子水， 加入 0. 0275g六偏 磷酸钠， 搅拌溶解后加入 50g l 0 m的氧化亚铜粉体， 超声分散 15min制 得稳定分散的氧化亚铜悬浊液；  First step: Add 100ml of deionized water to the round bottom flask, add 0. 0275g sodium hexametaphosphate, stir and dissolve, add 50g l 0m of cuprous oxide powder, and ultrasonically disperse for 15min to obtain stable dispersed oxide oxide. Copper suspension;
第二步： 将上述悬浊液移至磁力搅拌器中， 500rpm条件下将悬浊液 加热至 90 °C，把 pH值调节至 10，用蠕动泵把 100g/L的硫酸铜溶液 125ml 和 16g/L的氢氧化钠溶液缓慢滴加到悬浊液中， 包覆反应过程中保持 pH 值不变， 包覆反应时间为 2h， 继续搅拌直至冷却至室温， 然后过滤水洗 并在 50 Ό下烘干， 制得氧化铜包覆的氧化亚铜粉体。  Step 2: Transfer the above suspension to a magnetic stirrer, heat the suspension to 90 °C at 500 rpm, adjust the pH to 10, and use a peristaltic pump to apply 125 g and 16 g of 100 g/L copper sulfate solution. /L sodium hydroxide solution was slowly added dropwise to the suspension, the pH value was kept constant during the coating reaction, the coating reaction time was 2 h, stirring was continued until cooling to room temperature, then filtered and washed with water and dried at 50 Torr. Dry, copper oxide coated cuprous oxide powder is obtained.
最后说明实施例 1-3 的检测结果。  Finally, the detection results of Examples 1-3 will be described.
实施例 1-3 的检测结果方法为聚焦束离子技术。  The detection result of Examples 1-3 was a focused beam ion technique.
检测结果为在氧化亚铜粉体上包覆的氧化铜的厚度分别为：实施例 1 为 5nm， 实施例 2 为 25nm， 实施例 3 为 50nm。  As a result of the measurement, the thickness of the copper oxide coated on the cuprous oxide powder was 5 nm in Example 1, 25 nm in Example 2, and 50 nm in Example 3.
最后说明根据本发明所述的氧化亚铜表面包覆氧化铜的复合材料。 根据本发明所述的氧化亚铜表面包覆氧化铜的复合材料为依据前述 制备方法获得。  Finally, a composite material of copper oxide surface coated with copper oxide according to the present invention will be described. The copper oxide-coated composite material of the cuprous oxide surface according to the present invention is obtained in accordance with the aforementioned preparation method.
在根据本发明所述的氧化亚铜表面包覆氧化铜的复合材料中， 优选 地，氧化亚铜粉体的粒度为 50ηπ！〜 10 μ m，氧化亚铜表面包覆的氧化铜的 厚度为 5nm〜50nmc In the composite material in which the cuprous oxide surface is coated with copper oxide according to the present invention, preferably, the particle size of the cuprous oxide powder is 50ηπ! ~ 10 μ m, cuprous oxide coated with copper oxide Thickness is 5nm~50nm c

Claims

1. 一种氧化亚铜表面包覆氧化铜的复合材料的制备方法，包括歩骤: 将氧化亚铜粉体分散在含分散剂的去离子水中， 以制备悬浊液； 在规定温度、 规定 pH值下， 将铜盐溶液、 氢氧化钠溶液加入到悬浊 液中进行包覆反应，包覆反应过程中保持 pH值不变，以形成反应生成物， 所述反应生成物为氧化亚铜表面包覆氧化铜的复合材料； A method for preparing a composite material of copper oxide surface coated with copper oxide, comprising the steps of: dispersing a cuprous oxide powder in deionized water containing a dispersing agent to prepare a suspension; at a prescribed temperature, At the pH value, a copper salt solution and a sodium hydroxide solution are added to the suspension to carry out a coating reaction, and the pH value is maintained during the coating reaction to form a reaction product, and the reaction product is cuprous oxide. a composite material coated with copper oxide on the surface;
包覆反应之后， 冷却至室温；  After coating the reaction, cooling to room temperature;
对反应生成物进行过滤、 洗涤、 干燥。  The reaction product was filtered, washed, and dried.
2. 根据权利要求 1 所述的氧化亚铜表面包覆氧化铜的复合材料的 制备方法，其特征在于，在制备悬浊液时，氧化亚铜粉体的粒度为 50ηπ！〜 10 m; 氧化亚铜的浓度为 50g/L〜500g/L。  2. The method for preparing a copper oxide surface-coated copper oxide composite according to claim 1, wherein the particle size of the cuprous oxide powder is 50 ηπ when preparing the suspension! ~ 10 m; The concentration of cuprous oxide is 50g/L~500g/L.
3. 根据权利要求 1所述的氧化亚铜表面包覆氧化铜的复合材料的制 备方法， 其特征在于， 分散剂选自十二垸基苯磺酸钠、 十二垸基硫酸钠 或六偏磷酸钠或它们的混合物。  The method for preparing a copper oxide surface-coated copper oxide composite according to claim 1, wherein the dispersing agent is selected from sodium dodecylbenzenesulfonate, sodium dodecyl sulfate or six partial Sodium phosphate or a mixture thereof.
4. 根据权利要求 3所述的氧化亚铜表面包覆氧化铜的复合材料的制 备方法， 其特征在于， 分散剂的浓度为 0. 05 g/L〜0. 5 g/L。  。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。
5. 根据权利要求 1 所述的氧化亚铜表面包覆氧化铜的复合材料的 制备方法， 其特征在于， 所述规定温度范围为 70 °C〜90 °C， pH值范围为 8〜10， 包覆反应的时间为 0. 5〜2h。  The method for preparing a copper oxide surface-coated copper oxide composite according to claim 1, wherein the predetermined temperature range is 70 ° C to 90 ° C, and the pH ranges from 8 to 10, 5〜2小时。 The time of the coating reaction is 0. 5~2h.
6. 根据权利要求 1 所述的氧化亚铜表面包覆氧化铜的复合材料的 制备方法， 其特征在于， 所述铜盐溶液为硫酸铜溶液。  The method for preparing a copper oxide surface-coated copper oxide composite according to claim 1, wherein the copper salt solution is a copper sulfate solution.
7. 根据权利要求 6 所述的氧化亚铜表面包覆氧化铜的复合材料的 制备方法， 其特征在于， 硫酸铜溶液的浓度为 10g/L〜100g/L， 硫酸铜溶 液中所含的硫酸铜的量为氧化亚铜粉体质量的 5%〜25 /。，氢氧化钠溶液的 浓度为 4g/L〜16g/L。  The method for preparing a copper oxide surface-coated copper oxide composite according to claim 6, wherein the concentration of the copper sulfate solution is from 10 g/L to 100 g/L, and the sulfuric acid contained in the copper sulfate solution The amount of copper is 5% to 25 / of the mass of the cuprous oxide powder. The concentration of the sodium hydroxide solution is 4 g/L to 16 g/L.
8. 根据权利要求 1所述的氧化亚铜表面包覆氧化铜的复合材料的制 备方法，其特征在于，在所述复合材料中，氧化亚铜粉体的粒度为 50ηπ！〜 10 μ m, 氧化亚铜表面包覆的氧化铜的厚度为 5ηπ！〜 50nm。 8. The copper oxide surface-coated copper oxide composite material according to claim 1 The preparation method is characterized in that, in the composite material, the particle size of the cuprous oxide powder is 50ηπ! ~ 10 μ m, the thickness of copper oxide coated on the surface of cuprous oxide is 5ηπ! ~ 50nm.
9. 根据权利要求 1 所述的氧化亚铜表面包覆氧化铜的复合材料的 制备方法， 其特征在于， 在制备悬浊液时采用超声分散； 在将铜盐溶液、 氢氧化钠溶液加入到悬浊液中进行包覆反应过程中加有磁力搅拌。  9 . The method for preparing a copper oxide surface-coated copper oxide composite according to claim 1 , wherein ultrasonic dispersion is used in preparing the suspension; and the copper salt solution and the sodium hydroxide solution are added to Magnetic stirring was applied during the coating reaction in the suspension.
10. 一种氧化亚铜表面包覆氧化铜的复合材料，其依据权利要求 1-9 中任一项所述的氧化亚铜表面包覆氧化铜的复合材料的制备方法制备。  A composite material of a cuprous oxide surface-coated copper oxide, which is produced by the method for preparing a copper oxide surface-coated copper oxide composite according to any one of claims 1-9.
PCT/CN2013/075970 2012-05-21 2013-05-21 Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor WO2013174250A1 (en)

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