WO2017219382A1 - 一种双层ZnO空心球光催化材料及其制备方法 - Google Patents

一种双层ZnO空心球光催化材料及其制备方法 Download PDF

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WO2017219382A1
WO2017219382A1 PCT/CN2016/087811 CN2016087811W WO2017219382A1 WO 2017219382 A1 WO2017219382 A1 WO 2017219382A1 CN 2016087811 W CN2016087811 W CN 2016087811W WO 2017219382 A1 WO2017219382 A1 WO 2017219382A1
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hollow sphere
double
photocatalytic material
layer
zno
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祁秀秀
陈文华
刘巧云
张文雯
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常州工程职业技术学院
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

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  • the invention belongs to the technical field of photocatalytic materials and preparation thereof, and particularly relates to a double-layer ZnO hollow sphere photocatalytic material and a preparation method thereof.
  • a templating agent such as a carbon sphere or a silicon sphere is generally added to obtain a hollow structure, and then the template is removed by high temperature calcination to obtain a hollow structure.
  • a templating agent such as a carbon sphere or a silicon sphere is generally added to obtain a hollow structure, and then the template is removed by high temperature calcination to obtain a hollow structure.
  • high temperature firing may also result in cracking of the hollow structure and particle agglomeration.
  • a first aspect of the invention relates to a two-layer ZnO hollow sphere photocatalytic material comprising two ZnO inner and outer
  • the hollow sphere is composed of an inner hollow sphere having a diameter of 1.0 to 2.5 ⁇ m and an outer hollow sphere having a diameter of 1.5 to 4.5 ⁇ m.
  • a second aspect of the invention relates to a method for preparing a double-layer ZnO hollow sphere photocatalytic material, wherein the soluble zinc salt is dissolved in a mixture of monohydric alcohol and ethylene glycol to prepare a solution, and then the solution is sealed under conditions The solvothermal reaction is carried out to obtain the double-layer ZnO hollow sphere photocatalytic material.
  • solvent thermal reaction is derived from the “hydrothermal reaction”.
  • the hydrothermal reaction refers to a reaction in which a reaction mother liquid in which water is used as a solvent is subjected to autogenous pressure generated by heat under a closed condition.
  • solvent heat reaction the reaction of the reaction mother liquid under autogenous pressure generated by heat under a closed condition.
  • monohydric alcohol is used as a solvent
  • ethylene glycol is used as a morphology control agent
  • the mass of the ethylene glycol is 5% to 15% by mass of the monohydric alcohol.
  • the soluble zinc salt is zinc acetate or zinc nitrate or zinc sulfate, and the mass thereof is from 0.5% to 2.5% by mass of the monohydric alcohol.
  • the monohydric alcohol is ethanol.
  • the specific preparation method comprises the following steps:
  • Step 1 Adding a morphology control agent to the monohydric alcohol (selected anhydrous ethanol) to prepare a solvent, the mass ratio of the morphology control agent to the solvent is 5% to 15%, and after stirring for a certain period of time, the reaction raw material zinc acetate (Zn) (CH 3 COO) 2 ⁇ 2H 2 O), zinc nitrate (Zn(NO 3 ) 2 ⁇ 6H 2 O) or zinc sulfate (ZnSO 4 ) is dissolved in the above solvent to prepare a solution.
  • Zn zinc acetate
  • Zn(NO 3 ) 2 ⁇ 6H 2 O zinc nitrate
  • ZnSO 4 zinc sulfate
  • Step 3 After the end of step 2, the obtained product was centrifuged, and the product obtained by centrifugation was washed several times with absolute ethanol, and then dried at 60 ° C for 12 hours to obtain a double-layer ZnO hollow sphere.
  • the present invention prepares a double-layer ZnO hollow sphere by a one-step method for the first time.
  • the double-layer hollow structure can increase the specific surface area of the ZnO photocatalytic material, thereby increasing the active site of the photocatalytic reaction; the double-layer hollow structure can also improve the light.
  • the number of refraction/reflections in the double-layer hollow sphere improves the utilization efficiency of light. This makes the double-layer ZnO hollow sphere photocatalytic material have good photocatalytic performance in degrading organic pollutants, and can be widely used for environmental purification.
  • Example 1 is a (a) SEM image (b) TEM image of a double-layer ZnO hollow sphere prepared in Example 1 of the present invention.
  • Example 2 is an XRD spectrum of a double-layer ZnO hollow sphere prepared in Example 1 of the present invention.
  • Example 3 is a diagram showing the effect of photocatalytic degradation of phenol by ZnO prepared in Example 1 and Comparative Example of the present invention.
  • Figure 5 is a high resolution TEM image of a double layer ZnO hollow sphere prepared in Example 2 of the present invention.
  • Example 3 is a graph showing the effect of photocatalytic degradation of phenol by ZnO double-layer hollow spheres obtained in Example 1 and a comparative example, and compared with the comparative examples, the double-layer ZnO hollow spheres prepared in Example 1 were obtained under the same reaction time. Lower C/C 0 indicates better photocatalytic performance.

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Abstract

一种光催化材料及其制备，具体涉及一种双层ZnO空心球光催化材料，其由内外两个ZnO空心球构成，内层空心球直径为1.0～2.5μm，外层空心球直径1.5～4.5μm。还涉及该双层ZnO空心球光催化材料的制备方法：将可溶性锌盐溶解于一元醇和乙二醇的混合物中制成溶液，然后将该溶液在密闭条件下进行溶剂热反应，制得所述双层ZnO空心球光催化材料。

Description

一种双层ZnO空心球光催化材料及其制备方法 技术领域
本发明属于光催化材料及其制备技术领域，具体涉及一种双层ZnO空心球光催化材料及其制备方法。
背景技术
能源与环境问题是21世纪人类可持续发展面临的两大挑战。太阳能具有廉价、清洁、可再生等优点，因此，高效快捷的利用、转化和储存太阳能是各国研究者努力的目标。半导体光催化技术具有处理效率高，不存在二次污染等优点，能有效降解有毒有害污染物，在解决环境问题中具有广阔的应用前景。
氧化锌(ZnO)是一种禁带宽度为3.2eV的半导体材料，在紫外光照射下，ZnO可以被激发并产生光生电子-空穴对，从而进一步发生氧化还原反应。相比于常用的TiO2光催化剂，ZnO具有高的电子传输速率和长的光生载流子寿命，使其在光催化降解有机污染物、太阳能电池等领域具有广泛应用前景。此外，研究表明，多孔和空心结构对于提高光催化材料的活性有重要作用，一方面该结构可提供更多的活性位点，另一方面，空心结构也有利于光的反复折射和散射，提高光的利用率。
为了制备空心结构ZnO颗粒，在其制备过程中，一般会加入炭球或硅球等模板剂来得到空心结构，然后经过高温煅烧除去模板，获得空心结构。但是以上方法比较繁琐，无法通过一步法直接合成ZnO空心球。此外，高温焙烧也可能导致空心结构破裂和颗粒团聚。
双层ZnO空心球结构及其合成方法，之前从未有人报道过。
发明内容
本发明的目的在于提供一种在温和条件下一步合成双层ZnO空心球的方法。这种方法通过溶剂热法实现双层ZnO空心球的可控合成，制备工艺简单，条件温和，且对环境无污染。得到的双层ZnO空心球在光催化降解有机污染物方面具有很好的应用前景。
本发明的第一方面涉及一种双层ZnO空心球光催化材料，其由内外两个ZnO 空心球构成,内层空心球直径为1.0～2.5μm，外层空心球直径1.5～4.5μm。
本发明的第二方面涉及一种双层ZnO空心球光催化材料的制备方法，过程如下，将可溶性锌盐溶解于一元醇和乙二醇的混合物中制成溶液，然后将该溶液在密闭条件下进行溶剂热反应，制得所述双层ZnO空心球光催化材料。
其中“溶剂热反应”一词源自于“水热反应”。水热反应是指以水为溶剂的反应母液在密闭条件下在受热所产生的自生压力下进行的反应。当将反应溶剂由水改为其他溶剂时，反应母液在密闭条件下在受热所产生的自生压力下进行的反应，被称为“溶剂热反应”。
本发明中，一元醇作为溶剂，乙二醇作为形貌控制剂，乙二醇质量为一元醇质量的5％～15％。
优选地，所述可溶性锌盐为醋酸锌或硝酸锌或硫酸锌，其质量为一元醇质量的0.5％～2.5％。
优选地，溶剂热反应的温度范围为150～200℃，反应时间范围为1～24h。
优选地，所述一元醇为乙醇。
具体制备方法包括如下步骤：
步骤1：在一元醇(选无水乙醇)中加入形貌控制剂制成溶剂，形貌控制剂与溶剂的质量比例为5％～15％，搅拌一定时间后，将反应原料醋酸锌(Zn(CH3COO)2·2H2O)、硝酸锌(Zn(NO3)2·6H2O)或硫酸锌(ZnSO4)溶解在上述溶剂中制成溶液。
步骤2：将步骤1中配好的溶液移入水热釜内，密封后放入150～200℃烘箱中加热1～24小时后冷却至室温。
步骤3：步骤2结束后，将得到的产物离心，并将离心得到的产物用无水乙醇洗涤数次，然后在60℃下干燥12小时，得到双层ZnO空心球。
本发明具有以下优点：
1、本发明首次用一步法制备了双层ZnO空心球，双层空心结构可以提高ZnO光催化材料的比表面积，从而增加了光催化反应的活性位点；双层空心结构还可以提高光在双层空心球中的折射/反射次数，提高光的利用效率。这使得该双层ZnO空心球光催化材料在降解有机污染物方面具有很好的光催化性能，可以广泛用于环境净化。
2、本发明制备的双层ZnO空心球制备方法简单，容易操作，不需要加入模板剂再后处理等繁琐操作，产品制备成本低，制备条件温和，具有明显的经济效益，易于实现工业化生产，且对环境无污染。
附图说明：
图1为本发明实施例1制备的双层ZnO空心球的(a)SEM图像(b)TEM图像。
图2为本发明实施例1制备的双层ZnO空心球的XRD谱图。
图3为本发明实施例1和对比实施例制备的ZnO光催化降解苯酚效果图。
图4为对比实施例制备的ZnO的SEM图像。
图5为本发明实施例2所制备的双层ZnO空心球的高分辨率TEM图像。
具体实施方式：
下面结合附图对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。
实施例1
以150ml无水乙醇-乙二醇(乙二醇体积分数10％)混合溶液作为溶剂，室温下磁力搅拌半小时后，加入1.8g醋酸锌，搅拌半小时，待醋酸锌完全溶解后，将溶液移入水热釜中，放入烘箱中180℃下加热12小时，之后将产物离心，用离子水和无水乙醇洗涤数次，60℃下干燥12小时后得到ZnO双层空心球。
实施例2
以150ml无水乙醇-乙二醇(乙二醇体积分数10％)混合溶液作为溶剂，室温下磁力搅拌半小时后，加入1.8g硝酸锌，搅拌半小时，待硝酸锌完全溶解后，将溶液移入水热釜中，放入烘箱中180℃下加热12小时，之后将产物离心，并用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到双层ZnO空心球。
实施例3
以150ml无水乙醇-乙二醇(乙二醇体积分数10％)混合溶液作为溶剂，室温下磁力搅拌半小时后，加入1.8g硫酸锌，搅拌半小时，待硫酸锌完全溶解后，将溶液移入水热釜中，放入烘箱中180℃下加热12小时，之后将产物离心，并 用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到双层ZnO空心球。
对比实施例
作为对照例，以150ml纯无水乙醇作为溶剂，加入1.8g醋酸锌，搅拌半小时，待醋酸锌完全溶解后，将溶液移入水热釜中，放入烘箱中180℃下加热12小时，之后将产物离心，并用去离子水和无水乙醇洗涤数次。60℃下干燥12小时后得到ZnO。图1为得到对比实施例产品的SEM图像，可以看出，纯乙醇下得到的ZnO产品没有规则形貌。
实施例4
该实施例中，对实施例1和对比实施例所得的产品进行形貌表征和活性测试。其中以SEM和TEM观察产品形貌，以XRD来鉴别产品组成和晶型。图1为实施例1所得产品的SEM图像和TEM图像，可以看出，得到的ZnO为双层空心球结构。图2为实施例1所得双层空心球的XRD谱图，可以观测到明显的ZnO衍射峰。
光催化性能测试程序如下：在带有水冷夹套的反应器中加入100ml 40ppm的苯酚溶液，并加入20mg催化剂，超声30分钟后在黑暗条件下搅拌吸附20分钟达到吸附平衡。然后进行光照，光源为高压氙灯，水平放置于反应器上方，并控制反应液温度在25℃左右。每隔一段时间取样，离心分离后取上层清液用紫外-可见分光光度计分析降解前后的苯酚浓度，以C/C0来表示，其中C为某时刻的苯酚浓度，C0为苯酚的起始浓度，从而计算光照后溶液中苯酚的降解率。
图3为实施例1所得ZnO双层空心球和对照例制备的ZnO光催化降解苯酚效果图，与对比实施例相比，同等反应时间下，实施例1所制备的双层ZnO空心球所得的C/C0更低，说明其光催化性能更优异。

Claims (6)

  1. 一种双层ZnO空心球光催化材料，其特征在于，所述双层ZnO空心球光催化材料由内外两个ZnO空心球构成，内层空心球直径为1.0～2.5μm，外层空心球直径1.5～4.5μm。
  2. 一种双层ZnO空心球光催化材料的制备方法，其特征在于，将可溶性锌盐溶解于一元醇和乙二醇的混合物中制成溶液，然后将该溶液在密闭条件下进行溶剂热反应，制得所述双层ZnO空心球光催化材料。
  3. 根据权利要求2所述的制备方法，其特征在于，一元醇作为溶剂，乙二醇作为形貌控制剂，乙二醇质量为一元醇质量的5％～15％。
  4. 根据权利要求2所述的制备方法，其特征在于，所述可溶性锌盐为醋酸锌或硝酸锌或硫酸锌，其质量为一元醇质量的0.5％～2.5％。
  5. 根据权利要求2所述的制备方法，其特征在于，溶剂热反应的温度范围为150～200℃，反应时间范围为1～24h。
  6. 根据权利要求2所述的制备方法，其特征在于，所述一元醇为乙醇。
PCT/CN2016/087811 2016-06-21 2016-06-30 一种双层ZnO空心球光催化材料及其制备方法 WO2017219382A1 (zh)

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