CN111330601B - Preparation method of cuprous oxide composite material with core-shell structure - Google Patents
Preparation method of cuprous oxide composite material with core-shell structure Download PDFInfo
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Abstract
本发明公开了一种核壳结构的氧化亚铜复合材料的制备方法，其特征在于，包括：分别配制浓度为0.05～0.15mol/L的硫酸铜溶液和浓度为0.1～0.3mol/L亚硫酸钠溶液；在加热搅拌条件下将亚硫酸钠溶液加入到硫酸铜溶液中，得到混合溶液；将混合溶液陈化后进行固液分离；对固液分离后的固体进行洗涤干燥，得到核壳结构的氧化亚铜复合材料；本发明通过将硫酸铜溶液和亚硫酸钠溶液进行混合反应，通过控制反应过程，可以生成了一种新型具有核壳结构氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】，该复合材料的化学组成、形貌均不同于现有技术中以硫酸铜和亚硫酸钠为原料得到材料，且该复合材料在制备过程中不需要持续调节反应溶液中的pH值，降低了该复合材料的工业生产工艺条件。
The invention discloses a method for preparing a cuprous oxide composite material with a core-shell structure, which is characterized in that it comprises: respectively preparing a copper sulfate solution with a concentration of 0.05-0.15 mol/L and a sodium sulfite solution with a concentration of 0.1-0.3 mol/L ; Add sodium sulfite solution to copper sulfate solution under heating and stirring conditions to obtain a mixed solution; age the mixed solution and perform solid-liquid separation; wash and dry the solid after solid-liquid separation to obtain cuprous oxide with a core-shell structure Composite material; the present invention can generate a new type of cuprous oxide composite material with a core-shell structure [Cu 2 O@Cu 3 (SO 3 ) 2 · (H 2 O) 2 ], the chemical composition and morphology of the composite material are different from those obtained by using copper sulfate and sodium sulfite as raw materials in the prior art, and the composite material does not need to continuously adjust the reaction solution during the preparation process. The pH value reduces the industrial production process conditions of the composite material.
Description
【技术领域】【Technical field】
本发明属于氧化亚铜复合光催化材料技术领域，尤其涉及一种核壳结构的氧化亚铜复合材料的制备方法。The invention belongs to the technical field of cuprous oxide composite photocatalytic materials, and in particular relates to a preparation method of a cuprous oxide composite material with a core-shell structure.
【背景技术】【Background technique】
氧化亚铜半导体的带隙宽度约为2eV，可以有效的吸收太阳光中的可见光并在可见光的照射下能有效地产生光生载流子，且无毒性，在太阳能电池和光催化环境污染物降解等领域具有广泛的应用前景，但因其光电转换效率较低，这大大限制了其应用前景。非均相固体催化材料的催化性能主要与材料表面组成、形貌、活性位点的数量及活性等有关。氧化亚铜复合材料可以通过改变其表面组成、形貌、表面积与活性位点数及改善活性中心等来提高其光催化能力。因此，氧化亚铜复合材料弥补了氧化亚铜的缺陷，提高了氧化亚铜的光催化性能，拓宽了氧化亚铜的应用领域。The bandgap width of cuprous oxide semiconductor is about 2eV, which can effectively absorb visible light in sunlight and effectively generate photogenerated carriers under the irradiation of visible light, and is non-toxic. It can be used in solar cells and photocatalytic degradation of environmental pollutants, etc. The field has a wide range of application prospects, but its low photoelectric conversion efficiency greatly limits its application prospects. The catalytic performance of heterogeneous solid catalytic materials is mainly related to the surface composition, morphology, number and activity of active sites. Cuprous oxide composites can improve their photocatalytic ability by changing their surface composition, morphology, surface area and number of active sites and improving active centers. Therefore, the cuprous oxide composite material makes up for the defects of cuprous oxide, improves the photocatalytic performance of cuprous oxide, and broadens the application field of cuprous oxide.
现有文件中提出了一些制备氧化亚铜相关材料的方法，如：1.郭萍，郭璇利用亚硫酸钠还原硫酸铜制备；江西化工，2008(1)，52-53；2.张萍，刘恒，李大成亚硫酸钠还原法制备超细氧化亚铜粉末，四川有色金属，1998(2)，16-18；3.燕生虎，唐宽镇，张新涛利用亚硫酸钠还原法制备氧化亚铜粉的新技术，金川科技，2012(3)27-29。等。Some methods for preparing cuprous oxide-related materials are proposed in existing documents, such as: 1. Guo Ping, Guo Xuan use sodium sulfite to reduce copper sulfate to prepare; Jiangxi Chemical Industry, 2008 (1), 52-53; 2. Zhang Ping, Liu Heng, Li Dacheng, sodium sulfite reduction method to prepare ultra-fine cuprous oxide powder, Sichuan Nonferrous Metals, 1998 (2), 16-18; 3. Yan Shenghu, Tang Kuanzhen, Zhang Xintao New technology for preparation of cuprous oxide powder by sodium sulfite reduction method , Jinchuan Science and Technology, 2012 (3) 27-29. Wait.
但是，上述技术的制备过程中必须严格控制反应溶液的pH值，且文献中所提到的pH值最高不超过5.5，即实验反应过程中需要实时调节pH值，但是，这是一项难度非常大的操作工艺，因为在该实验反应过程中，pH一直是在动态变化的，在反应过程中必须实时跟踪监测并持续调整反应溶液的pH值，这对于工业生产来讲是难以实现的。However, the pH value of the reaction solution must be strictly controlled in the preparation process of the above technology, and the pH value mentioned in the literature does not exceed 5.5, that is, the pH value needs to be adjusted in real time during the experimental reaction process, but this is a very difficult task. Large operating process, because in the experimental reaction process, the pH has been changing dynamically, and it is necessary to track and monitor in real time and continuously adjust the pH value of the reaction solution during the reaction process, which is difficult to achieve in terms of industrial production.
【发明内容】【Content of invention】
本发明的目的是提供一种核壳结构的氧化亚铜复合材料的制备方法，在制备过程中不需要持续调节溶液的pH值，降低工业生产的工艺条件，核壳结构氧化亚铜复合材料在材料颗粒表面组成以【Cu3(SO3)2·(H2O)2】为主，催化时以【Cu3(SO3)2·(H2O)2】为主导，【Cu2O】起辅助作用。The purpose of the present invention is to provide a method for preparing a cuprous oxide composite material with a core-shell structure. In the preparation process, it is not necessary to continuously adjust the pH value of the solution, and reduce the process conditions of industrial production. The cuprous oxide composite material with a core-shell structure is The surface composition of material particles is dominated by [Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ], and [Cu 3 (SO 3 ) 2 ·(H 2 O ) ] play an auxiliary role.
本发明采用以下技术方案：一种核壳结构的氧化亚铜复合材料的制备方法，其特征在于，包括：The present invention adopts the following technical scheme: a method for preparing a cuprous oxide composite material with a core-shell structure, characterized in that it includes:
分别配制浓度为0.05～0.15mol/L的硫酸铜溶液和浓度为0.1～0.3mol/L亚硫酸钠溶液；Prepare respectively a copper sulfate solution with a concentration of 0.05-0.15 mol/L and a sodium sulfite solution with a concentration of 0.1-0.3 mol/L;
在加热搅拌条件下将亚硫酸钠溶液加入到硫酸铜溶液中，得到混合溶液；The sodium sulfite solution is added to the copper sulfate solution under heating and stirring to obtain a mixed solution;
将混合溶液陈化后进行固液分离；Carry out solid-liquid separation after the mixed solution is aged;
对固液分离后的固体进行洗涤干燥，得到核壳结构的氧化亚铜复合材料。The solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a core-shell structure.
进一步地，硫酸铜溶液和亚硫酸钠溶液的物质的量浓度比为1:2。Further, the substance concentration ratio of the copper sulfate solution and the sodium sulfite solution is 1:2.
进一步地，亚硫酸钠溶液的体积大于硫酸铜溶液的体积。Further, the volume of the sodium sulfite solution is greater than that of the copper sulfate solution.
进一步地，当亚硫酸钠溶液加入到硫酸铜溶液中时，保持硫酸铜溶液的温度为80～84℃。Further, when the sodium sulfite solution is added to the copper sulfate solution, keep the temperature of the copper sulfate solution at 80-84°C.
进一步地，固液分离的具体方法为抽滤。Further, the specific method of solid-liquid separation is suction filtration.
进一步地，对固液分离后的固体进行洗涤干燥包括：Further, washing and drying the solid after solid-liquid separation includes:
用纯水对固体洗涤3次，在将洗涤后的固体在100℃下干燥。The solid was washed three times with pure water, and the washed solid was dried at 100°C.
进一步地，方法包括：Further, the method includes:
称取CuSO4·5H2O溶于纯水，配成浓度为0.1mol/L的硫酸铜溶液；Weigh CuSO 4 5H 2 O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.1mol/L;
称取Na2SO3溶于纯水，配成浓度为0.2mol/L的亚硫酸钠溶液；Dissolve Na2SO3 in pure water to form a sodium sulfite solution with a concentration of 0.2mol / L;
将硫酸铜溶液加入到反应容器中，机械搅拌，预热至81℃并保持该反应温度；Add copper sulfate solution into the reaction vessel, stir mechanically, preheat to 81°C and maintain the reaction temperature;
向硫酸铜溶液中加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得到核壳结构的氧化亚铜复合材料。Add sodium sulfite solution to the copper sulfate solution, finish adding within 30 minutes, age for 30 minutes, filter with suction, wash with pure water three times, and dry at 100°C to obtain a cuprous oxide composite material with a core-shell structure.
进一步地，方法包括：Further, the method includes:
称取CuSO4·5H2O溶于纯水，配成浓度为0.05mol/L的硫酸铜溶液；Weigh CuSO 4 5H 2 O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.05mol/L;
称取Na2SO3溶于纯水，配成浓度为0.1mol/L的亚硫酸钠溶液；Weigh Na 2 SO 3 and dissolve it in pure water to make a sodium sulfite solution with a concentration of 0.1mol/L;
将硫酸铜溶液加入到反应容器中，机械搅拌，预热至82℃并保持该反应温度；Add the copper sulfate solution into the reaction vessel, stir mechanically, preheat to 82°C and maintain the reaction temperature;
向硫酸铜溶溶液中加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得到核壳结构的氧化亚铜复合材料。Add sodium sulfite solution to the copper sulfate solution, finish adding within 30 minutes, age for 30 minutes, filter with suction, wash with pure water three times, and dry at 100°C to obtain a cuprous oxide composite material with a core-shell structure.
进一步地，方法包括：Further, the method includes:
称取CuSO4·5H2O溶于纯水，配成浓度为0.15mol/L的硫酸铜溶液；Weigh CuSO 4 5H 2 O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.15mol/L;
称取Na2SO3溶于纯水，配成浓度为0.3mol/L的亚硫酸钠溶液；Dissolve Na2SO3 in pure water to form a sodium sulfite solution with a concentration of 0.3mol / L;
将硫酸铜溶液加入到反应容器中，机械搅拌，预热至83～84℃并保持该反应温度；Add the copper sulfate solution into the reaction vessel, stir it mechanically, preheat to 83-84°C and keep the reaction temperature;
向硫酸铜溶液中加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得到核壳结构的氧化亚铜复合材料。Add sodium sulfite solution to the copper sulfate solution, finish adding within 30 minutes, age for 30 minutes, filter with suction, wash with pure water three times, and dry at 100°C to obtain a cuprous oxide composite material with a core-shell structure.
本发明的有益效果是：本发明通过将硫酸铜溶液和亚硫酸钠溶液进行混合反应，通过控制反应过程，可以生成了一种新型具有核壳结构氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】，该复合材料的化学组成、形貌均不同于现有技术中以硫酸铜和亚硫酸钠为原料得到材料，且该复合材料在制备过程中不需要持续调节反应溶液中的pH值，降低了该复合材料的工业生产工艺条件。The beneficial effects of the present invention are: the present invention can generate a new type of cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ], the chemical composition and morphology of the composite material are different from the materials obtained from copper sulfate and sodium sulfite in the prior art, and the composite material does not need continuous adjustment during the preparation process The pH value in the reaction solution reduces the industrial production process conditions of the composite material.
【附图说明】【Description of drawings】
图1为本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】的制备工艺流程图；Figure 1 is a flow chart of the preparation process of the cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] with a core-shell structure in an embodiment of the present invention;
图2为本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】样品的XRD图；Fig. 2 is an XRD pattern of a cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] sample with a core-shell structure in an embodiment of the present invention;
图3为本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】样品分散性的SEM图；Fig. 3 is an SEM image of the sample dispersion of the cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] with a core-shell structure in an embodiment of the present invention;
图4为本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】样品的SEM核壳结构图；Fig. 4 is a SEM core-shell structure diagram of a cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] sample with a core-shell structure in an embodiment of the present invention;
图5为本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】样品的EDS能谱图；Fig. 5 is the EDS energy spectrum of the cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] sample with core-shell structure in the embodiment of the present invention;
图6本发明实施例中具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】与葡萄糖还原得到的氧化亚铜材料在可见光下对甲基橙的催化降解图谱。Fig. 6 The cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] with a core-shell structure in the embodiment of the present invention is compared with the cuprous oxide material obtained by reducing glucose under visible light. Catalytic degradation profile of methyl orange.
【具体实施方式】【Detailed ways】
下面结合附图和具体实施方式对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.
本发明公开了一种核壳结构的氧化亚铜复合材料的制备方法，如图1所示，包括以下步骤：The invention discloses a method for preparing a cuprous oxide composite material with a core-shell structure, as shown in Figure 1, comprising the following steps:
分别配制浓度为0.05～0.15mol/L的硫酸铜溶液和浓度为0.1～0.3mol/L亚硫酸钠溶液；在加热搅拌条件下将亚硫酸钠溶液加入到硫酸铜溶液中，得到混合溶液；将混合溶液陈化后进行固液分离；对固液分离后的固体进行洗涤干燥，得到核壳结构的氧化亚铜复合材料。Prepare a copper sulfate solution with a concentration of 0.05-0.15mol/L and a sodium sulfite solution with a concentration of 0.1-0.3mol/L respectively; add the sodium sulfite solution to the copper sulfate solution under heating and stirring to obtain a mixed solution; age the mixed solution Finally, solid-liquid separation is carried out; the solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a core-shell structure.
本发明通过将硫酸铜溶液和亚硫酸钠溶液进行混合反应，通过控制反应过程，可以生成了一种新型具有核壳结构氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】，该复合材料的化学组成、形貌均不同于现有技术中以硫酸铜和亚硫酸钠为原料得到材料，且该复合材料在制备过程中不需要持续调节反应溶液中的pH值，降低了该复合材料的工业生产工艺条件。In the present invention, a novel cuprous oxide composite material with a core-shell structure [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 ( 2) 2 ], the chemical composition and appearance of this composite material are all different from the materials obtained in the prior art with copper sulfate and sodium sulfite as raw materials, and the composite material does not need to continuously adjust the pH value in the reaction solution during the preparation process, The industrial production process conditions of the composite material are reduced.
在本发明中，硫酸铜溶液和亚硫酸钠溶液的浓度不易太大，因为浓度过大时颗粒状容易团聚，就形成了多孔结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】，难以形成核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】。In the present invention, the concentration of copper sulfate solution and sodium sulfite solution is not easy to be too high, because when the concentration is too high, the particles are easy to agglomerate, and a cuprous oxide composite material with a porous structure is formed [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ], cuprous oxide composite material that is difficult to form a core-shell structure [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ].
在本发明中，硫酸铜溶液和亚硫酸钠溶液的物质的量浓度比为1:2。亚硫酸钠溶液的体积大于硫酸铜溶液的体积(优选的消耗的亚硫酸钠溶液的体积与硫酸铜溶液的体积比为3:2)，且在本发明中亚硫酸钠加入速度较慢，所以，溶液中硫酸铜是过量的，溶液处于酸性环境，pH小于4。反应时，首先生成氧化亚铜颗粒，随着亚硫酸钠溶液的加入，pH值逐渐升高，当pH大于5后，开始生成Cu3(SO3)2·(H2O)2，新生成的Cu3(SO3)2·(H2O)2，因颗粒小具有较大的表面能而吸附在Cu2O颗粒表面以降低其表面能，形成具有核壳结构的复合材料【Cu2O@Cu3(SO3)2·(H2O)2】。In the present invention, the substance concentration ratio of copper sulfate solution and sodium sulfite solution is 1:2. The volume of sodium sulfite solution is greater than the volume of cupric sulfate solution (the volume of preferred consumed sodium sulfite solution is 3:2 with the volume ratio of cupric sulfate solution), and sodium sulfite adds slower in the present invention, so, copper sulfate in solution is In excess, the solution is in an acidic environment with a pH less than 4. During the reaction, cuprous oxide particles are first formed , and with the addition of sodium sulfite solution, the pH value gradually increases. 3 (SO 3 ) 2 ·(H 2 O) 2 is adsorbed on the surface of Cu 2 O particles to reduce the surface energy due to the small particle size and large surface energy, forming a composite material with a core-shell structure [Cu 2 O@ Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ].
具体的，当亚硫酸钠溶液加入到硫酸铜溶液中时，保持硫酸铜溶液的温度为80～84℃。固液分离的具体方法选择为抽滤，抽滤方式更适合大规模的工业应用，能提高产量。Specifically, when the sodium sulfite solution is added to the copper sulfate solution, keep the temperature of the copper sulfate solution at 80-84°C. The specific method of solid-liquid separation is suction filtration, which is more suitable for large-scale industrial applications and can increase production.
作为一种具体的实施方式，对固液分离后的固体进行洗涤干燥采用以下方式：As a specific embodiment, the following methods are used for washing and drying the solid after solid-liquid separation:
用纯水对固体洗涤3次，在将洗涤后的固体在100℃下干燥。The solid was washed three times with pure water, and the washed solid was dried at 100°C.
本发明得到的具有核壳结构的复合材料【Cu2O@Cu3(SO3)2·(H2O)2】，粒度较大，易于洗涤且洗涤无损失，有利于产业化。整个工艺过程操作简单产品易洗涤，能最大程度的利用原料、节省原料，反应终点易于控制，同时，整个过程不需要考虑控制溶液的pH值，大大地降低了工艺难度，没有引入其它原料，减少了环境污染，有效提升产能。The composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] with a core-shell structure obtained in the present invention has a large particle size, is easy to wash without loss, and is beneficial to industrialization. The whole process is simple to operate and the product is easy to wash, which can maximize the use of raw materials and save raw materials. The reaction end point is easy to control. At the same time, the whole process does not need to consider controlling the pH value of the solution, which greatly reduces the difficulty of the process. Reduce environmental pollution and effectively increase production capacity.
实施例1：Example 1:
称取12.5gCuSO4·5H2O溶于纯水配成500mL溶液(硫酸铜浓度为0.1mol/L)，称取18.9gNa2SO3溶于纯水配成750mL溶液(亚硫酸钠浓度为0.2mol/L)，将硫酸铜溶液加入到2L的烧杯中，机械搅拌，预热至81℃并保持该反应温度条件下，加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得产品。Weigh 12.5g CuSO 4 ·5H 2 O and dissolve in pure water to make 500mL solution (copper sulfate concentration is 0.1mol/L), weigh 18.9gNa 2 SO 3 and dissolve in pure water to make 750mL solution (sodium sulfite concentration is 0.2mol/L L), add copper sulfate solution into a 2L beaker, stir mechanically, preheat to 81°C and keep the reaction temperature, add sodium sulfite solution, finish adding within 30min, age for 30min, suction filter, wash with pure water for 3 times, dried at 100°C to obtain the product.
实施例2：Example 2:
称取6.25gCuSO4·5H2O溶于纯水配成500mL溶液(硫酸铜浓度为0.05mol/L)，称取9.5gNa2SO3溶于纯水配成750mL溶液(亚硫酸钠浓度为0.1mol/L)，将硫酸铜溶液加入到2L的烧杯中，机械搅拌，预热至82℃并保持该反应温度条件下，加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得产品。Weigh 6.25g CuSO 4 ·5H 2 O and dissolve in pure water to make 500mL solution (copper sulfate concentration is 0.05mol/L), weigh 9.5gNa 2 SO 3 and dissolve in pure water to make 750mL solution (sodium sulfite concentration is 0.1mol/L L), add copper sulfate solution into a 2L beaker, stir mechanically, preheat to 82°C and keep the reaction temperature, add sodium sulfite solution, finish adding within 30min, age for 30min, suction filter, wash with pure water for 3 times, dried at 100°C to obtain the product.
实施例3：Example 3:
称取18.8gCuSO4·5H2O溶于纯水配成500mL溶液(硫酸铜浓度为0.15mol/L)，称取28.5gNa2SO3溶于纯水配成750mL溶液(亚硫酸钠浓度为0.3mol/L)，将硫酸铜溶液加入到2L的烧杯中，机械搅拌，预热至83℃并保持该反应温度条件下，加入亚硫酸钠溶液，30min内加完，陈化30min，抽滤，纯水洗涤3次，100℃干燥，得产品。Weigh 18.8g CuSO 4 5H 2 O and dissolve in pure water to make 500mL solution (copper sulfate concentration is 0.15mol/L), weigh 28.5gNa 2 SO 3 and dissolve in pure water to make 750mL solution (sodium sulfite concentration is 0.3mol/L L), add copper sulfate solution into a 2L beaker, stir mechanically, preheat to 83°C and keep the reaction temperature, add sodium sulfite solution, finish adding within 30min, age for 30min, suction filter, wash with pure water for 3 times, dried at 100°C to obtain the product.
实施例4：Example 4:
称取18.8gCuSO4·5H2O溶于纯水配成500mL溶液(硫酸铜浓度为0.15mol/L)，称取28.5gNa2SO3溶于纯水配成750mL溶液(亚硫酸钠浓度为0.3mol/L)，将硫酸铜溶液加入到2L的烧杯中，机械搅拌，预热至84℃并保持该反应温度条件下，加入亚硫酸钠溶液，25min内加完，陈化30min，抽滤，纯水洗涤4次，105℃干燥，得产品。Weigh 18.8g CuSO 4 5H 2 O and dissolve in pure water to make 500mL solution (copper sulfate concentration is 0.15mol/L), weigh 28.5gNa 2 SO 3 and dissolve in pure water to make 750mL solution (sodium sulfite concentration is 0.3mol/L L), add copper sulfate solution into a 2L beaker, stir mechanically, preheat to 84°C and keep the reaction temperature, add sodium sulfite solution, finish adding within 25min, age for 30min, suction filter, wash with pure water for 4 Once dried at 105°C, the product was obtained.
参见图2，这是本发明最佳实施例1的XRD图，根据图谱中显示衍射峰的峰位，对照PDF卡片可知，左侧的峰数据与PDF卡片编号11-0240的数据一致，可归属于Cu3(SO3)2·(H2O)2的衍射峰，晶面指数分别为(-101)，(002)和(112)。Referring to Fig. 2, this is the XRD pattern of the best embodiment 1 of the present invention. According to the peak position of the diffraction peak shown in the spectrum, compared with the PDF card, the peak data on the left is consistent with the data of the PDF card number 11-0240, which can be attributed to According to the diffraction peaks of Cu 3 (SO 3 ) 2 ·(H 2 O) 2 , the plane indices are (-101), (002) and (112), respectively.
对照PDF卡片，右侧的峰数据与PDF卡片编号99-0041的数据一致，可归属于立方相Cu2O的衍射峰，晶面指数分别为(111)，(200)和(220)。由此，证明该实施例中得到的样品组成为Cu2O@Cu3(SO3)2·(H2O)2的复合材料。Compared with the PDF card, the peak data on the right is consistent with the data of PDF card No. 99-0041, which can be attributed to the diffraction peak of cubic phase Cu 2 O, and the crystal plane indices are (111), (200) and (220) respectively. Thus, it is proved that the composition of the sample obtained in this example is a composite material of Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 .
参见图3，为本发明实施例1中样品分散性的SEM图，从图中可以看出该样品为2μm球形颗粒及其团聚成小于10μm的团聚体。Referring to FIG. 3 , it is an SEM image of the dispersion of the sample in Example 1 of the present invention. It can be seen from the figure that the sample is a spherical particle of 2 μm and agglomerated into agglomerates smaller than 10 μm.
参见图4，为本发明实施例1中样品的SEM核壳结构图，从图中可以看出该样品为核壳结构材料。Referring to FIG. 4 , it is a SEM core-shell structure diagram of the sample in Example 1 of the present invention. It can be seen from the figure that the sample is a core-shell structure material.
如图5所示，图5a中核为铜、氧两种元素构成；图5b中壳为铜、硫、氧三种元素构成，进一步证明了该发明得到的样品组成为Cu2O@Cu3(SO3)2·(H2O)2的具有核壳结构的复合材料。As shown in Figure 5, the core in Figure 5a is composed of two elements of copper and oxygen; the shell in Figure 5b is composed of three elements of copper, sulfur and oxygen, which further proves that the composition of the sample obtained by this invention is Cu 2 O@Cu 3 ( SO 3 ) 2 ·(H 2 O) 2 composite material with core-shell structure.
本发明既解决了上述技术实施过程中工艺条件难以控制的技术难题，又制备出易于产业化的光催化性能优异的新型核壳结构氧化亚铜复合材料。核壳结构氧化亚铜复合材料在材料颗粒表面组成以【Cu3(SO3)2·(H2O)2】为主(从图2中可以得到证明)，催化时以【Cu3(SO3)2·(H2O)2】为主导，【Cu2O】起辅助作用。本发明工艺简单，操作方便，原料来源易得，工艺流程简单，得到的产品易洗涤。The invention not only solves the technical problem that the process conditions are difficult to control during the implementation of the above technology, but also prepares a novel core-shell structure cuprous oxide composite material that is easy to industrialize and has excellent photocatalytic performance. The surface composition of the core-shell cuprous oxide composite material is mainly [Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] (it can be proved from Figure 2), and [Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] is dominant, and [Cu 2 O] plays an auxiliary role. The invention has simple process, convenient operation, easy-to-obtain raw material source, simple process flow and easy washing of the obtained product.
通过相同条件下的甲基橙可见光光催化降解实验，如图6所示，本发明实施例中得到的具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】在光照180min时甲基橙光催化降解率达到91.2％，而葡萄糖还原新鲜氢氧化铜得到的氧化亚铜材料在光照180min时甲基橙的光催化降解率只有67.7％。Through the visible light photocatalytic degradation experiment of methyl orange under the same conditions, as shown in Figure 6, the cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 · (H 2 O) 2 ] The photocatalytic degradation rate of methyl orange reached 91.2% under 180 min of light irradiation, while the photocatalytic degradation rate of methyl orange was only 67.7% under 180 min of light irradiation for the cuprous oxide material obtained by reducing fresh copper hydroxide with glucose .
所以，本发明实施例中得到的具有核壳结构的氧化亚铜复合材料【Cu2O@Cu3(SO3)2·(H2O)2】的光催化降解甲基橙的能力明显优于普通氧化亚铜材料。Therefore, the cuprous oxide composite material [Cu 2 O@Cu 3 (SO 3 ) 2 ·(H 2 O) 2 ] with a core-shell structure obtained in the examples of the present invention is obviously superior in the photocatalytic degradation of methyl orange. In ordinary cuprous oxide materials.
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