CN105664906A - 一种ZnO反蛋白石结构光催化薄膜的制备方法 - Google Patents
一种ZnO反蛋白石结构光催化薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种ZnO反蛋白石结构光催化薄膜的制备方法。该方法首先以甲基丙烯酸甲酯、过硫酸铵为原料，制备聚甲基丙烯酸甲酯(PMMA)微球；然后将PMMA微球分散在水中，采用热蒸发自组装方式制备PMMA微球组装蛋白石薄膜；最后以PMMA微球组装蛋白石薄膜为模板，将硝酸锌水/乙醇溶液滴加到模板上，自然渗透后在室温中干燥，再经过高温煅烧，得到ZnO反蛋白石结构薄膜。本发明制备方法原料简单，制备周期较短，得到的蛋白石结构薄膜具有良好的光催化性能，可使亚甲基蓝在紫外光下完全降解，且利于回收，能反复使用，薄膜与基底之间有良好的结合力。
Description
技术领域
本发明涉及一种ZnO反蛋白石结构光催化薄膜的制备方法，该方法在光子晶体、光催化降解有机污染物领域具有重要应用。
背景技术
基于反蛋白石结构的薄膜为光催化降解有机污染物提供了一种行之有效的新方法。利用这种反蛋白石结构的薄膜能有效提高光催化降有机污染物的效率。
基于反蛋白石结构的氧化锌薄膜为光催化降解有机污染物提供了一种新的途径，为发展高性能的光催化剂提供有用的信息。已发现的包括氧化锌在内的大多数光催化剂禁带宽度位于紫外区，只能吸收紫外光。然而提高催化剂对可见光的利用是提高催化效率的目前催化领域正在探索的问题。谢娟等在ActaPhys.-Chim.Sin.,2011,27(1):193-198中报道了利用胶体自组装法得到了粒径可控的蛋白石结构ZnO薄膜。所得的ZnO自组装薄膜具有可调控的可见光波段的光子带隙，实现ZnO在太阳光照射下光催化降解甲基橙溶液并取得良好的效果。3D反蛋白石结构是一种重复的面心立方的壳结构，相比于蛋白石结构的氧化锌薄膜，反蛋白石结构的氧化锌薄膜具有以下特点：同样具有可控的可见光波段的光子带隙；反蛋白石结构的氧化锌具有大量的有序的球形孔隙，由于其多孔特点，为吸附有机污染物提供很大的表面积，促进了物的运输提高了光捕获效率。此外，S.Meng在RSCAdv.,2013,3,17021.中报道了通过控制布拉格衍射光、多重散射和慢光子效应的光的传播，这种有序的3D反蛋白石结构能提供一个额外的光子效率以增加光和物质相互作用。以上作用说明3D反蛋白石结构作为催化剂有着一定的优势。
目前制备反蛋白石结构的方法有多种，包括垂直沉积法、电气化学法、化学气相沉积法等。垂直沉积法相较于电气化学法和化学沉积法有着操作简单、成本低廉等优点。
发明内容
为了克服现有技术的不足，本发明的目的在提供一种ZnO反蛋白石结构光催化薄膜的制备方法。其工艺简单，原料易得。本发明制备得到的反蛋白石结构的ZnO可用来提高光催化降解有机污染物效率。
本发明提供了一种ZnO反蛋白石结构光催化薄膜的制备方法，其是先以微乳液聚合法制备出聚甲基丙烯酸甲酯(PMMA)亚微米小球，再采用垂直沉积法自组装得到PMMA的薄膜，再以此为模板，制备出ZnO反蛋白石结构的薄膜。
本发明是这样实施的：先称量一定比例的甲基丙烯酸甲酯MMA、过硫酸铵水溶液置于容器中，采用微乳液聚合法进行反应，通过调节甲基丙烯酸甲酯与过硫酸铵的量的比例，得到不同粒径的PMMA亚微米小球，并将其分散到介电溶液中形成分散液；其次量取一定量的分散液于容器中，将玻璃片置于容器中，采用垂直沉积法制备得到PMMA小球自组装的蛋白石结构的薄膜；然后以此作为模板，将配置好的硝酸锌—水-乙醇溶液滴加到模板上进行渗透，常温干燥，再经过高温煅烧，得到ZnO反蛋白石结构薄膜。本发明的技术方案具体如下介绍。
一种ZnO反蛋白石结构光催化薄膜的制备方法，具体步骤如下：
(1)聚甲基丙烯酸甲酯PMMA微球的制备
以甲基丙烯酸甲酯MMA、过硫酸铵水溶液为起始原料，采用微乳液聚合法制备聚甲基丙烯酸甲酯PMMA微球；
(2)蛋白石结构薄膜的制备
先将聚甲基丙烯酸甲酯PMMA微球分散到高纯水中得到分散液，再将亲水处理后的玻璃片垂直置于容器中，通过垂直沉积法制得PMMA微球组装的薄膜，再在120～130℃温度下干燥30～40分钟，得到模板；
(3)反蛋白石结构氧化锌薄膜的制备
将硝酸锌、水和乙醇配成的溶液滴加到模板上进行渗透，常温干燥，然后在400～500℃温度下煅烧1～2h，再自然降至室温，得到ZnO反蛋白石结构光催化薄膜。
上述步骤(1)中，过硫酸铵水溶液的浓度为8-10wt％，甲基丙烯酸甲酯MMA与过硫酸铵水溶液的体积比为4：5～15:5。
上述步骤(1)中，微乳液聚合法中的反应温度为80～100℃，反应时间为2～3h。
上述步骤(1)中，得到的聚甲基丙烯酸甲酯PMMA微球的粒径为250～500nm。
上述步骤(2)中，聚甲基丙烯酸甲酯PMMA微球在高纯水的质量百分数为0.1％～2％。
上述步骤(2)中，玻璃片的亲水处理方法如下：先用丙酮超声10～20min,再用乙醇超声10～20min，之后用过氧化氢-硫酸溶液处理10-20min，优选的，过氧化氢和硫酸的体积比3:2.
上述步骤(2)中，垂直沉积法的温度为50～60℃，时间为2～3天。
上述步骤(3)中，硝酸锌和乙醇的质量体积比为0.5:3～3:3g/ml,乙醇和水的体积比为4:2-2:2。
上述步骤(3)中，以1～2℃/min的升温速率升到400～500℃。
本发明的有益效果在于：本发明制备方法原料简单，制备周期较短，得到的蛋白石结构薄膜具有良好的光催化性能，可使亚甲基蓝在紫外光下完全降解，且利于回收，能反复使用；此外薄膜与基底之间有良好的结合力，对研究光子晶体结构增强光催化降解有机污染物性能具有重要的参考价值。
附图说明
图1为不同放大倍数的PMMA胶体球自组装扫描电镜图。
图2为不同粒径PMMA胶体球组装薄膜的自组装数码照片图。
图3为不同放大倍数的ZnO反蛋白石结构的扫描电镜图。
图4为ZnO反蛋白石结构薄膜的XRD图。
图5为不同催化时间催化降解有机污染物(亚甲基蓝)的紫外-可见光谱图(a、暗吸附；b,10min；c,20min；d,30min；e,40min；f,50min；g,60min；h,70min；i,80min；j,90min；k,100min；l,110min；)。
图6为光催化降解有机污染物(亚甲基蓝)浓度比图。
具体实施方式
下面结合附图和实施例对本发明技术方案进行详细阐述。
实施例1
取甲基丙烯酸甲酯和10wt％过硫酸铵水溶液，其体积比为4:5，为起始原料，采用微乳液聚合法在80℃下反应3h，通入氮气，制备得到PMMMA(平均粒径为300nm)。按0.1％质量百分比将其分散到高纯水中得到分散液。取一定量分散液置于容器中，将进行过处理的玻璃片垂直置于容器中，通过垂直沉积法(温度50℃，时间3d)自组装得到PMMA亚微米小球的蛋白石结构薄膜，令其高温120℃干燥40min，以此薄膜作为模板。将溶有0.5g硝酸锌的100ml乙醇-水(体积比2:3)溶液滴加到模板上进行渗透，将其常温干燥，再经过高温400℃(升温速率为1℃/min，保温时间为2h，自然降温)煅烧，得到氧化锌的反蛋白石结构薄膜。图1是PMMA小球的不同放大倍数扫描电镜图。
实施例2
取甲基丙烯酸甲酯和10wt％过硫酸铵水溶液，其体积比为10:5，为起始原料，采用微乳液聚合法在90℃下反应2h，通入氮气，制备得到PMMMA(平均粒径为320nm)。按0.1％质量百分比将其分散到高纯水中得到分散液。取一定量分散液置于容器中，将进行过处理的玻璃片垂直置于容器中，通过垂直沉积法(温度60℃，时间2d)自组装得到PMMA亚微米小球的蛋白石结构薄膜，令其高温120℃干燥40min，以此薄膜作为模板。将溶有0.5g硝酸锌的100ml乙醇-水(体积比2:3)溶液滴加到模板上进行渗透，将其常温干燥，再经过高温500℃(升温速率为1℃/min，保温时间为2h，自然降温)煅烧，得到氧化锌的反蛋白石结构薄膜。图2是不同粒径PMMA胶体球自组装数码照片图；图3是不同放大倍数的ZnO反蛋白石结构的扫描电镜图。
实施例3
取甲基丙烯酸甲酯和10wt％过硫酸铵水溶液，其体积比为15:5，为起始原料，采用微乳液聚合法在90℃下反应2h，通入氮气，制备得到PMMMA(平均粒径为450nm)。按0.1％质量百分比将其分散到高纯水中得到分散液。取一定量分散液置于容器中，将进行过处理的玻璃片垂直置于容器中，通过垂直沉积法(温度50℃，时间3d)自组装得到PMMA亚微米小球的蛋白石结构薄膜，令其高温130℃干燥30min，以此薄膜作为模板。将溶有3g硝酸锌的100ml乙醇-水(体积比2:3)溶液滴加到模板上进行渗透，将其常温干燥，再经过高温450℃(升温速率为1℃/min，保温时间为2h，自然降温)煅烧，得到氧化锌的反蛋白石结构薄膜。图4是ZnO反蛋白石结构薄膜的XRD图。
应用实施例
测试条件：紫外光照射范围(30-800nm)，亚甲基蓝浓度为5ppm，图5是催化降解有机污染物(亚甲基蓝)的紫外-可见光谱图，图中664nm处为亚甲基蓝的特征吸收峰，随着催化时间的延长，特征峰值逐渐降低，经过110min降解效率接近100％。说明有机物被有效降解；图6是光催化降解有机污染物(亚甲基蓝)浓度比图，随着时间的推移，亚甲基蓝浓度逐渐降低；同时从光催化降解有机污染物实验取样数码照片看，随着催化时间的推移，蓝色逐渐变淡，也说明浓度逐渐降低。
Claims (9)
1.一种ZnO反蛋白石结构光催化薄膜的制备方法，其特征在于，具体步骤如下：
(1)聚甲基丙烯酸甲酯PMMA微球的制备
以甲基丙烯酸甲酯MMA、过硫酸铵水溶液为起始原料，采用微乳液聚合法制备聚甲基丙烯酸甲酯PMMA微球；
(2)蛋白石结构薄膜的制备
先将聚甲基丙烯酸甲酯PMMA微球分散到高纯水中得到分散液，再将亲水处理后的玻璃片垂直置于容器中，通过垂直沉积法制得PMMA微球组装的薄膜，再在120～130℃温度下干燥30～40分钟，得到模板；
(3)反蛋白石结构氧化锌薄膜的制备
将硝酸锌、水和乙醇配成的溶液滴加到模板上进行渗透，常温干燥，然后在400～500℃温度下煅烧1～2h，再自然降至室温，得到ZnO反蛋白石结构光催化薄膜。
2.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，过硫酸铵水溶液的浓度为8-10wt％，甲基丙烯酸甲酯MMA与过硫酸铵水溶液的体积比为4：5～15:5。
3.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，微乳液聚合法中的反应温度为80～100℃，反应时间为2～3h。
4.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，得到的聚甲基丙烯酸甲酯PMMA微球的粒径为250～500nm。
5.根据权利要求1所述的制备方法，其特征在于：步骤(2)中，聚甲基丙烯酸甲酯PMMA微球在高纯水的质量百分数为0.1％～2％。
6.根据权利要求1所述的制备方法，其特征在于：步骤(2)中，玻璃片的亲水处理方法如下：先用丙酮超声10～20min,再用乙醇超声10～20min，之后用过氧化氢-硫酸溶液处理10-20min。
7.根据权利要求1所述的制备方法，其特征在于：步骤(2)中，垂直沉积法的温度为50～60℃，时间为2～3天。
8.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，硝酸锌和乙醇的质量体积比为0.5:3～3:3g/ml,乙醇和水的体积比为4:2-2:2。
9.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，以1～2℃/min的升温速率升到400～500℃。
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