CN112156769A - 一种Al/WO3 纳米复合薄膜及其制备方法和应用 - Google Patents
一种Al/WO3 纳米复合薄膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种Al/WO3纳米复合薄膜及其制备方法和应用，该Al/WO3纳米复合薄膜的制备方法包括：提供WO3基底，然后通过磁控溅射在所述WO3基底上负载Al，所述WO3基底为水热法制备的海胆状纳米WO3薄膜材料。本发明所提供的简易制备Al/WO3纳米复合薄膜的方法，具有镀膜效率高、纯度高、溅射产物与基底结合力强、薄膜结构紧密稳定、成膜均匀性好且可精确控制的优点。
Description
技术领域
本发明涉及纳米材料的制备技术领域，尤其涉及一种Al/WO3纳米复合薄膜及其制备方法和应用。
背景技术
三氧化钨(WO3)半导体的禁带宽度约为2.4-2.8eV，作为光催化剂使用时，在可见光激发下即可产生光生电子和空穴参与氧化还原反应，因其原料丰富易制备，价带空穴具有强氧化能力，在酸性条件下稳定性好，耐光腐蚀，无毒和成本低越来越受到科研人员的关注。但WO3单独作为光催化剂使用时还面临着光生载流子复合较快、紫外-可见光波段吸收有限的问题。
贵金属负载(如Au、Ag和Pt等)是提升WO3光响应性能的有效方法之一，金属作为助催化剂可以促进光生载流子分离，而且其具有的局域表面等离子体共振(LSPR)特性可以产生局域增强场和高能热电子，引发对入射光的强吸收从而提高光能利用率，但贵金属比较稀缺和昂贵，大规模应用受到限制，并且在紫外光波段无法产生LSPR效应。Al作为地壳中储量最大的金属元素，来源广泛，价格低廉，并且具有高的等离子体能量(约15.6eV)和高电子密度，其LSPR波长范围可在紫外-近红外光谱区域进行调节，能覆盖较大的可见光区域。但目前对于Al/WO3纳米复合薄膜制备和性能的研究非常少。
发明内容
本发明实施例提供一种Al/WO3纳米复合薄膜的制备方法，该方法具有镀膜效率高、纯度高、溅射产物与基底结合力强、薄膜结构紧密稳定、成膜均匀性好且可精确控制的优点。
本发明实施例提供一种Al/WO3纳米复合薄膜的制备方法，包括：提供WO3基底，然后通过磁控溅射在所述WO3基底上负载Al，所述WO3基底为水热法制备的海胆状纳米WO3薄膜材料。本发明所提供的简易制备Al/WO3纳米复合薄膜的方法，具有效率高、纯度高、溅射产物与基底结合力强、薄膜结构紧密稳定、均匀性好且可精确控制工艺参数的优点。
发明人经研究发现，通过控制磁控溅射的时间和水热法的参数，可以获得不同形貌的Al/WO3纳米复合薄膜，尤其是，目前为光催化剂使用的WO3材料及其与金属复合的二元光催化材料，一般是粉末状的纳米颗粒，存在着在环境应用时较为分散，不易回收，再生性差，重复使用率低，容易引起二次污染的技术难题，本领域中目前还没有固载型的金属/WO3复合纳米薄膜材料，而用湿化学法制备的纳米金属材料很难实现与WO3材料构成复合薄膜。本发明通过采用特定的WO3纳米结构基体与Al纳米颗粒二者复合而成的成纳米复合薄膜材料还可循环使用，避免粉体形式催化剂不易回收、流失危害环境，具有环境友好的特点。
在一些实施例中，所述磁控溅射包括以下步骤：
1)放置所述WO3基底和Al靶材，并通入惰性气体；
2)调节电流和电压至溅射功率为100～200W，在所述WO3基底上溅射Al。
在一些实施例中，步骤1)中，所述惰性气体为Ar气，所述Ar气的气体流量为10～30sccm；和/或，溅射气压控制在0.3～0.8Pa；优选的，所述Ar气的气体流量为25sccm，溅射气压控制在0.5Pa。
在一些实施例中，步骤2)中，在WO3基底材料上溅射Al的溅射时间控制在20min以内；优选的，所述溅射时间为10～20min。本发明中，使基片台匀速旋转，在WO3基底上溅射Al不同时间，溅射反应完成后，取出所述复合薄膜材料，降温至室温留待使用。
在一些实施例中，步骤2)中，所述溅射功率为130～145W；优选的，调节所述电流为0.2～0.5A，所述电压为380～480V。本发明中，开启直流溅射电源，调节电流I和电压V至所需溅射功率W(W＝I×V)，优选的方案中，所述电流为0.3A，所述电压为450V；和/或，溅射功率为135W。
在一些实施例中，所述WO3基底材料的制备包括：以钨酸铵为钨源，以柠檬酸为控形剂，在预处理后的FTO玻璃上进行水热反应。
在一些实施例中，所述水热反应的反应温度为160～190℃；和/或，所述水热反应的反应时间为10～15h；优选的，所述水热反应的反应温度为180℃；和/或，所述水热反应的反应时间为12h。
在一些实施例中，所述FTO玻璃的预处理包括：
S1、将NaOH、水和丙酮混合，制得前处理液；
S2、将FTO玻璃放入所述前处理液中，进行超声处理，清洗、干燥；其中，所述NaOH、水和丙酮的质量体积比为0.5～2g：5～20ml：10～30ml；和/或，所述超声处理的时间为5～30min；所述干燥的温度为40～65℃；优选的，所述NaOH、水和丙酮的质量体积比为1.5g：10ml：20ml；和/或，所述超声处理的时间为20min；所述干燥的温度为60℃。
根据本发明，以钨酸铵为钨源，柠檬酸为控形剂，在特定水热反应条件下获得海胆状纳米WO3基底材料。进一步在上述制备产物基础上采用优选条件下的磁控溅射方法负载金属Al颗粒及Al纳米棒，所得到的Al纳米结构能有均予地覆盖在WO3基底材料的表面，并且实现Al与WO3的界面结合，得到Al/WO3纳米复合薄膜材料，所制备的Al/WO3纳米复合薄膜具有形貌稳定、尺寸分布较均匀和方便回收二次利用等优点，能很好解决粉末形式催化剂带来的环境问题，可应用于污染物降解等光催化领域。
本发明实施例还提供所述的Al/WO3纳米复合薄膜的制备方法制备得到的Al/WO3纳米复合薄膜。
本发明实施例还提供所述的Al/WO3纳米复合薄膜的制备方法制备得到的Al/WO3纳米复合薄膜或所述的Al/WO3纳米复合薄膜作为光催化材料的应用。
本发明的有益效果至少在于：
(1)本发明提供了一种简易的Al/WO3纳米复合薄膜的制备方法，该方法具有镀膜效率高、纯度高、溅射产物与基底结合力强、薄膜结构紧密稳定、成膜均匀性好且可精确控制工艺参数的优点；
(2)本发明所制备的Al/WO3纳米复合薄膜具有形貌稳定、尺寸分布较均匀和固载形式方便回收再利用等优点，能很好解决粉末形式催化剂因回收不完全的二次污染的环境问题，可应用于污染物降解等光催化领域。
附图说明
图1为本发明实施例1所制备的海胆状WO3基底材料的SEM图(放大倍率为4000倍)；
图2为本发明实施例1所制备的海胆状WO3基底材料的SEM图(放大倍率为20000倍)；
图3为本发明实施例1所制备的磁控溅射Al 10min后的Al/WO3纳米复合薄膜SEM图(放大倍率为10000倍)；
图4为本发明实施例1所制备的磁控溅射Al 10min后的Al/WO3纳米复合薄膜SEM图(放大倍率为50000倍)；
图5为本发明实施例1所制备的磁控溅射Al 10min后的Al/WO3纳米复合薄膜EDS图；
图6为本发明实施例2所制备的磁控溅射Al 15min后的Al/WO3纳米复合薄膜SEM图(放大倍率为10000倍)；
图7为本发明实施例2所制备的磁控溅射Al 15min后的Al/WO3纳米复合薄膜SEM图(放大倍率为50000倍)；
图8为本发明实施例3所制备的磁控溅射Al 20min后的Al/WO3纳米复合薄膜SEM图(放大倍率为10000倍)。
图9为本发明实施例3所制备的磁控溅射Al 20min后的Al/WO3纳米复合薄膜SEM图(放大倍率为50000倍)。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。
本发明中，所用仪器等未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。所述方法如无特别说明均为常规方法，所述原材料如无特别说明均能从公开商业途径而得。本发明中，所用的磁控溅射设备为JCP-350M3高真空多靶磁控溅射镀膜，北京泰科诺科技有限公司。
实施例1
本实施例提供一种称取0.931g钨酸铵和0.192g柠檬酸溶于15ml去离子水中，混合搅拌20min获得WO3前驱体溶液；将预处理后的FTO玻璃和上述前驱体溶液置入水热釜中于180℃保温12h，反应完成后取出、干燥，即可获得WO3基底材料。
具体地，所述FTO玻璃的预处理过程如下：
S1、称取1.5g NaOH溶于10ml水和20ml丙酮中，超声混合制得NaOH的丙酮-水前处理液；
S2、将FTO玻璃置入前处理液中，超声处理20min，取出后用去离子水反复清洗并在60℃下干燥即得。
取WO3基底材料和高纯Al靶材置于磁控溅射设备的基片台和靶材座上，通入高纯Ar气，调节气体流量为25sccm，使溅射腔室达到所需真空度，溅射气压控制在0.5Pa。开启直流溅射电源，调节电流为0.3A、电压为450V，此时溅射功率为135W。打开基片台旋转按钮，使放置在基片台上的WO3基底材料匀速旋转，以Ar气为主离化气体进行辉光放电，使高纯Al靶材溅射出Al粒子生长沉积在WO3基底上，溅射时间为10min，形成Al/WO3纳米复合薄膜。
图1-图2为本发明实施例1所制备的海胆状WO3基底材料的SEM图(图1放大倍率为4000倍，图2放大倍率为20000倍)，三维海胆状WO3是由纳米棒组装而成，纳米棒表面光滑；图3-图4为磁控溅射Al 10min后的Al/WO3纳米复合薄膜SEM图(图3放大倍率为10000倍，图4放大倍率为50000倍)，从图中可以看出，溅射Al并未改变海胆状WO3基底的形貌，并且有细小的Al颗粒分布在WO3纳米棒上。图5为磁控溅射Al 10min后的Al/WO3纳米复合薄膜EDS图，样品只含W、O和Al元素，无其他杂质存在，说明复合材料纯度较高，其中Al元素均匀分布在WO3上，证实了Al/WO3纳米复合薄膜的形成。
实施例2
取WO3基底材料和高纯Al靶材置于磁控溅射设备的基片台和靶材座上，通入高纯Ar气，调节气体流量为25sccm，使溅射腔室达到所需真空度，溅射气压控制在0.5Pa。开启直流溅射电源，调节电流为0.3A、电压为450V，此时溅射功率为135W。打开基片台旋转按钮，使放置在基片台上的WO3基底材料匀速旋转，以Ar气为主离化气体进行辉光放电，使高纯Al靶材溅射出Al粒子生长沉积在WO3基底上，溅射时间为15min，形成Al/WO3纳米复合薄膜。
图6-图7为本发明实施例2所制备的磁控溅射Al 15min后的Al/WO3纳米复合薄膜SEM图，其中图6放大倍率为10000倍，图7放大倍率为50000倍，从图中可以看出，在海胆状WO3基底上溅射Al 15min后，Al的形貌由Al颗粒变化为Al纳米棒，Al/WO3纳米复合薄膜的形貌呈树枝状分布。
实施例3
取WO3基底材料和高纯Al靶材置于磁控溅射设备的基片台和靶材座上，通入高纯Ar气，调节气体流量为25sccm，使溅射腔室达到所需真空度，溅射气压控制在0.5Pa。开启直流溅射电源，调节电流为0.3A、电压为450V，此时溅射功率为135W。打开基片台旋转按钮，使放置在基片台上的WO3基底材料匀速旋转，以Ar气为主离化气体进行辉光放电，使高纯Al靶材溅射出Al粒子生长沉积在WO3基底上，溅射时间为20min，形成Al/WO3纳米复合薄膜。
图8-图9为本发明实施例3所制备的磁控溅射Al 20min后的Al/WO3纳米复合薄膜SEM图，其中图8放大倍率为10000倍，图9放大倍率为50000倍，从图中可以看出，在海胆状WO3基底上溅射Al更长时间后，WO3基底几乎完全被Al覆盖，复合材料表面更加粗糙。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
Claims (10)
1.一种Al/WO3纳米复合薄膜的制备方法，其特征在于，包括：提供WO3基底，然后通过磁控溅射在所述WO3基底上负载Al，所述WO3基底为水热法制备的海胆状纳米WO3薄膜材料。
2.根据权利要求1所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，所述磁控溅射包括以下步骤：
1)放置所述WO3基底和Al靶材，并通入惰性气体；
2)调节电流和电压至溅射功率为100～200W，在所述WO3基底上溅射Al。
3.根据权利要求2所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，步骤1)中，所述惰性气体为Ar气，所述Ar气的气体流量为10～30sccm；和/或，溅射气压控制在0.3～0.8Pa。
4.根据权利要求2或3所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，步骤2)中，在WO3基底材料上溅射Al的溅射时间控制在20min以内；优选的，所述溅射时间为10～20min。
5.根据权利要求4所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，步骤2)中，所述溅射功率为130～145W。
6.根据权利要求1所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，所述WO3基底材料的制备包括：以钨酸铵为钨源，以柠檬酸为控形剂，在预处理后的FTO玻璃上进行水热反应。
7.根据权利要求7所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，所述水热反应的反应温度为160～190℃；和/或，所述水热反应的反应时间为10～15h。
8.根据权利要求6或7所述的Al/WO3纳米复合薄膜的制备方法，其特征在于，所述FTO玻璃的预处理包括：
S1、将NaOH、水和丙酮混合，制得前处理液；
S2、将FTO玻璃放入所述前处理液中，进行超声处理，清洗、干燥；其中，所述NaOH、水和丙酮的质量体积比为0.5～2g：5～20ml：10～30ml；和/或，所述超声处理的时间为5～30min；所述干燥的温度为40～65℃。
9.权利要求1-8任一项所述的Al/WO3纳米复合薄膜的制备方法制备得到的Al/WO3纳米复合薄膜。
10.权利要求1-8任一项所述的Al/WO3纳米复合薄膜的制备方法制备得到的Al/WO3纳米复合薄膜或权利要求9所述的Al/WO3纳米复合薄膜作为光催化材料的应用。
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