CN111992226B - 一种光催化纳米复合催化剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种光催化分解水的纳米复合催化剂及其制备方法，属于光催化纳米材料的合成技术领域，实现了在紫外—可见光催化下的纯水分解反应，所述催化剂具有很好的催化活性和稳定性；而且制备工艺操作简单，反应条件温和，所用试剂价格低廉。本发明涉及了一种光催化纳米材料La,Al双金属离子共掺SrTiO3作为光催化吸光半导体材料的设计和制备方法，并担载WS2@CrOx为析氢助催化剂，CoOOH为析氧助催化剂，La,Al摩尔占比分别为1%~10%，以及助催化剂担载量为0.5wt%‑5wt%的不同WS2@CrOx/La,Al‑SrTiO3/CoOOH复合纳米材料。
Description
技术领域
本发明属于光催化纳米材料的合成技术领域，具体涉及一种光催化纳米复合催化剂及其制备方法。
背景技术
半导体光催化在温和条件下能促成多类困难的化学反应有利进行，例如光催化降解有机物、光催化合成氨、甲醇及其它高附加值的化工原料，光催化分解水等，这被认为是一种将光子能量转化为化学能的关键技术。由于氢具有较高的燃烧热值和环境友好性，被认为是一种清洁的替代能源，2mol的水分解可生成2mol的氢气和1mol氧气，在以光能源的利用为前提转化成可存储的氢能时，光催化纯水分解技术就以很高的水准可能替代化石燃料的纯粹消耗机制，因而成为研究热门。但是水分解反应是一个热力学上的“爬坡”过程，分解水占用的大比重能耗致使水分解产氢的策略无法大面积投入实际生产。
自从1972年Fujishima和Honda利用金红石型TiO2阳极和铂阴极进行光电化学的水分解以来，人们一直致力于构建高效的多相光催化的研究。到目前为止，已经有大量的半导体光催化剂被研究出来，如硫化物(CdS)、氮化物(Ta3N5)和金属氧化物(TiO2)等。SrTiO3具有简单的立方钙钛矿结构，还原后为n型半导体，禁带宽度为3.2eV。在研究早期，SrTiO3已经被一些尝试证明可以作为光电极电解水产氢。截至目前，SrTiO3基半导体材料又被证实可在无偏压下转化太阳能进行纯水分解。然而如何促进光生载流子的激发，以及载流子的分离和迁移效率的进一步提高，都是目前该领域研究是重中之重。
有许多手段用于改善材料的光催化活性，其中元素掺杂是最常用的手段之一。许多研究表明SrTiO3结构存在本征缺陷，Ti3+的存在降低了其催化活性；研究发现Rh3+金属离子掺杂可以提升SrTiO3材料的光催化活性，但几次光激发循环后易导致Rh4+价态的形成，致使光催化活性降低；日本东京大学Domen等报导，Al3+单一金属离子掺杂SrTiO3光催化剂展示了很高的光催化活性，但由于Al3+占据Ti位后，导致SrTiO3基半导体整体电荷不平衡，从而造成催化活性和稳定性下降。而有研究表面，Sr2+阳离子位的金属离子取代，如La3+，则有利于Rh3+掺杂到SrTiO3晶体结构中并稳定其结构晶型，降低了形成能从而提高了析氢速率。
此外，提升光催化水分解活性的重要手段之一是担载析氢端和析氧端助催化剂，用以加速电子—空穴对的分离。常用的析氢助催化剂有Pt、Rh、Ru等贵金属，析氧助催化剂有IrOx、CoOx等。由于贵金属催化剂储量稀少，价格昂贵，且具有很大的功函数，在光催化水分解中的氧还原逆反应较为明显，致使光催化纯水分解效率低下。
发明内容
本发明提供了一种光催化纳米复合催化剂及其制备方法，所述催化剂为La,Al双金属离子共掺SrTiO3并担载WS2@CrOx和CoOOH为助催化剂，所述催化剂具有很好的催化活性和稳定性；而且制备工艺操作简单，反应条件温和，所用试剂价格低廉。
为实现以上目的，本发明采用以下技术方案：
一种光催化纳米复合催化剂，所述催化剂为La、Al双金属离子共掺SrTiO3，并担载WS2@CrOx为析氢助催化剂，CoOOH为析氧助催化剂。
以上所述催化剂中，La和Al元素的摩尔占比分别为1％～10％，La和Al的摩尔比相等，所述析氢助催化剂担载量为0.5wt％-5wt％，所述析氧助催化剂担载量为0.5wt％-5wt％。
一种光催化纳米复合催化剂的制备方法，包括以下步骤：
(1)将等量摩尔比的含镧化合物和含铝化合物与SrTiO3纳米颗粒均匀球磨混合1～24小时；
(2)将步骤(1)中球磨混合好的含镧化合物、含铝化合物和SrTiO3再与过量SrCl2均匀搅拌后，于800-1300℃保温4-12小时；
(3)将步骤(2)高温热处理后的样品处理出去多余的SrCl2，干燥后得到La,Al-SrTiO3纳米颗粒；
(4)将步骤(3)得到的La,Al-SrTiO3纳米颗粒与WS2纳米片以及铬盐均匀研磨混合1-4小时，在惰性气体保护下，200-500℃保温1-5小时，得到WS2@CrOx担载量为0.5wt％-5wt％的WS2@CrOx/La,Al-SrTiO3；
(5)将步骤(4)得到的WS2@CrOx/La,Al-SrTiO3置于一定浓度的Co盐水溶液中，紫外光源照射下反应1-10小时，在WS2@CrOx/La,Al-SrTiO3表面生成担载量为0.5wt％-5wt％的CoOOH纳米颗粒，水洗过滤烘干后得到WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料。
以上所述步骤中，步骤(1)中所述含镧化合物的摩尔比为1％～10％，所述含铝化合物的摩尔比为1％～10％，所述的含镧化合物为氧化镧、碳酸镧、醋酸镧、硝酸镧、氯化镧中的一种或多种，所述含铝化合物为氧化铝、碳酸铝、醋酸铝、硝酸铝、氯化铝中的一种或多种；
步骤(3)中所述La,Al-SrTiO3纳米颗粒尺寸为200-500纳米；
步骤(4)中所述WS2纳米片为一定量的(NH4)2WS4 800℃热解剥离后形成的，所述的铬盐化合物为硝酸铬、氯化铬、乙酸铬中的一种或多种；
步骤(5)中所述Co盐为硝酸钴、氯化钴、硫酸钴、醋酸钴中的一种或多种。
有益效果：本发明提供了一种光催化纳米复合催化剂及其制备方法，所述催化剂为La,Al双金属离子共掺SrTiO3并担载WS2@CrOx为析氢助催化剂，CoOOH为析氧助催化剂，相比于单一金属离子如Al掺杂SrTiO3材料以及其他双金属离子掺杂SrTiO3材料，本发明的催化剂具有更稳定的结构；本发明合成的WS2@CrOx/La,Al-SrTiO3/CoOOH材料不需要担载贵金属助催化剂，实现在紫外—可见光下的光催化反应，光催化分解水的反应中还能实现可见光下分解纯水，并且在光催化反应中具有很好的催化活性和稳定性；而且本发明工艺操作简单，反应条件温和，所用试剂价格低廉。
附图说明
图1是本发明实施例1制得的WS2@CrOx/La,Al-SrTiO3/CoOOH透射电镜图；
图2是本发明实施例3制得的WS2@CrOx/La,Al-SrTiO3/CoOOH光催化水分解活性图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细的说明：
实施例1
一种光催化纳米复合催化剂的制备方法，包括以下步骤：
分别称取0.008mol的硝酸镧、0.008mol的硝酸铝和0.084mol的SrTiO3，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于球磨机中，4000转速下球磨10h，再加入1mol的SrCl2继续球磨1h；将球磨后的混合物过筛分离，并置于马弗炉中，在800度下保温12小时，取出后用大量去离子水抽滤洗涤，随后将材料置于干燥箱中80度过夜干燥，即得到La,Al-SrTiO3纳米颗粒；将La,Al-SrTiO3与占质量比2.0wt％的(NH4)2WS4 800度热解剥离后形成的WS2纳米片以及铬盐均匀研磨混合4小时，在惰性气体保护下，500度保温4小时，得到WS2@CrOx/La,Al-SrTiO3；再将WS2@CrOx/La,Al-SrTiO3复合材料置于0.05M的Co盐水溶液中，紫外光源照射下反应5小时，在其表面生成担载量为5wt％的CoOOH纳米颗粒，最后经过水洗过滤，烘干后得到WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料。
上述制备方法得到的WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料的透射电镜图如图1所示，纳米颗粒尺寸为200-300纳米。
实施例2
一种光催化纳米复合催化剂的制备方法，包括以下步骤：
分别称取0.005mol的硝酸镧、0.005mol的硝酸铝和0.09mol的SrTiO3，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于球磨机中，4000转速下球磨24h，再加入1mol的SrCl2继续球磨1h；将球磨后的混合物过筛分离，并置于马弗炉中，在1000度下保温8小时；取出后用大量去离子水抽滤洗涤，随后将材料置于干燥箱中80度过夜干燥，即得到La,Al-SrTiO3纳米催化剂材料；将La,Al-SrTiO3与占质量比1.0wt％的(NH4)2WS4 400度热解剥离后形成的WS2纳米片以及铬盐均匀研磨混合4小时，在惰性气体保护下，400度保温2小时，得到WS2@CrOx/La,Al-SrTiO3；再将WS2@CrOx/La,Al-SrTiO3复合材料置于0.05M的Co盐水溶液中，紫外光源照射下反应10小时，在其表面生成担载量为5wt％的CoOOH纳米颗粒，最后经过水洗过滤，烘干后得到WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料。
实施例3
一种光催化纳米复合催化剂的制备方法，包括以下步骤：
分别称取0.001mol的硝酸镧、0.001mol的硝酸铝和0.098mol的SrTiO3，在玛瑙研钵中混合研磨1h，将研磨后的混合物置于球磨机中，4000转速下球磨24h，再加入1mol的SrCl2继续球磨1h；将球磨后的混合物过筛分离，并置于马弗炉中，在800度下保温4小时；取出后用大量去离子水抽滤洗涤，随后将材料置于干燥箱中80度过夜干燥，即得到La,Al-SrTiO3纳米催化剂材料；将La,Al-SrTiO3与占质量比0.5wt％的(NH4)2WS4 400度热解剥离后形成的WS2纳米片以及铬盐均匀研磨混合4小时，在惰性气体保护下，500度保温4小时，得到WS2@CrOx/La,Al-SrTiO3；再将WS2@CrOx/La,Al-SrTiO3复合材料置于0.05M的Co盐水溶液中，紫外光源照射下反应1小时，在其表面生成担载量为5wt％的CoOOH纳米颗粒，最后经过水洗过滤，烘干后得到WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料，所述光催化剂为La,Al双金属离子共掺SrTiO3，并担载WS2@CrOx为析氢助催化剂和CoOOH为析氧助催化剂。
将上述制备方法得到的WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料用于在300W氙灯紫外-可见全光谱照射纯水中测试其光催化水分解性能，纯水200mL，催化剂用量为20mg，光源为300WXe灯，光催化分解水的效果如图2所示，氢气生成速率为498μmol/g/h，氧气生成速率为242μmol/g/h，氢气氧气摩尔量析出比接近2：1。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下还可以作出若干改进，这些改进也应视为本发明的保护范围。
Claims (9)
1.一种光催化纳米复合催化剂，其特征在于，所述催化剂为La、Al双金属离子共掺SrTiO3，并担载WS2@CrOx和CoOOH作为助催化剂。
2.根据权利要求1所述的光催化纳米复合催化剂，其特征在于，所述La、Al摩尔占比分别为1％～10％，所述WS2@CrOx担载量为0.5wt％-5wt％，所述CoOOH担载量为0.5wt％-5wt％。
3.根据权利要求1或2所述的光催化纳米复合催化剂，其特征在于，所述La和Al的摩尔比相等。
4.一种光催化纳米复合催化剂的制备方法，其特征在于，包括以下步骤：
(1)将等量摩尔比的含镧化合物和含铝化合物与SrTiO3纳米颗粒均匀球磨混合1～24小时；
(2)将步骤(1)中球磨混合好的含镧化合物、含铝化合物和SrTiO3再与过量SrCl2均匀搅拌后，于800-1300℃保温4-12小时；
(3)将步骤(2)得到的样品处理除去多余的SrCl2，干燥后得到La,Al-SrTiO3纳米颗粒；
(4)将步骤(3)得到的La,Al-SrTiO3纳米颗粒与WS2纳米片以及铬盐均匀研磨混合1-4小时，在惰性气体保护下，200-500℃保温1-5小时，得到WS2@CrOx担载量为0.5wt％-5wt％的WS2@CrOx/La,Al-SrTiO3；
(5)将步骤(4)得到的WS2@CrOx/La,Al-SrTiO3置于一定浓度的Co盐水溶液中，紫外光源照射下反应1-10小时，在WS2@CrOx/La,Al-SrTiO3表面生成担载量为0.5wt％-5wt％的CoOOH纳米颗粒，水洗过滤烘干后得到WS2@CrOx/La,Al-SrTiO3/CoOOH纳米复合催化剂材料。
5.根据权利要求4所述的光催化纳米复合催化剂的制备方法，其特征在于，步骤(1)中所述含镧化合物的摩尔比为1％～10％，所述含铝化合物的摩尔比为1％～10％。
6.根据权利要求4或5所述的光催化纳米复合催化剂的制备方法，其特征在于，步骤(1)中所述的含镧化合物为氧化镧、碳酸镧、醋酸镧、硝酸镧、氯化镧中的一种或多种，所述含铝化合物为氧化铝、碳酸铝、醋酸铝、硝酸铝、氯化铝中的一种或多种。
7.根据权利要求4所述的光催化纳米复合催化剂的制备方法，其特征在于，步骤(3)中所述La,Al-SrTiO3纳米颗粒尺寸为200-500纳米。
8.根据权利要求4所述的光催化纳米复合催化剂的制备方法，其特征在于，步骤(4)中所述WS2纳米片为(NH4)2WS4 800℃热解剥离后形成的，所述的铬盐化合物为硝酸铬、氯化铬、乙酸铬中的一种或多种。
9.根据权利要求4所述的光催化纳米复合催化剂的制备方法，其特征在于，步骤(5)中所述Co盐为硝酸钴、氯化钴、硫酸钴、醋酸钴中的一种或多种。
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