CN112023938B - 一种双金属离子掺杂的纳米复合光催化剂及其制备方法 - Google Patents
一种双金属离子掺杂的纳米复合光催化剂及其制备方法 Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 21
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- 238000000034 method Methods 0.000 claims description 3
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- 229940009827 aluminum acetate Drugs 0.000 claims description 2
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- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
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- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
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Abstract
本发明公开了一种双金属离子掺杂的纳米复合光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，所述的光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。本发明以La源和Al源化合物按比例与SrTiO3和SrCl2均匀混合，在一定温度下热处理，再经大量水洗，除去多余SrCl2，烘干后得到目标产物，得到的光催化剂为La,Al双金属离子共掺SrTiO3，担载RhCrOx和CoOOH作为助催化剂，其中La摩尔占比为1%~10%，Al摩尔占比为1%~10%，La和Al为等摩尔比，制备得到的光催化剂能够实现可见光下的纯水分解。
Description
技术领域
本发明属于光催化纳米材料的合成技术领域，尤其涉及一种双金属离子掺杂的纳米复合光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，2 mol的水分解可生成2 mol的氢气和1 mol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3.2 eV。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。
发明内容
本发明提供了一种双金属离子掺杂的纳米复合光催化剂及其制备方法，所述的光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：
一种双金属离子掺杂的纳米复合光催化剂，所述光催化剂为La,Al双金属离子共掺SrTiO3，并担载RhCrOx和CoOOH作为助催化剂，所述La摩尔占比为1%~10%，Al摩尔占比为1%~10%，所述La和Al为等摩尔比，所述RhCrOx和CoOOH的担载量为1.0wt%。
一种双金属离子掺杂的纳米复合光催化剂的制备方法，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洗涤除去多余的SrCl2，干燥后得到La,Al-SrTiO3纳米颗粒；
（4）将步骤（3）合成的La,Al-SrTiO3纳米颗粒与一定量的NaRhCl6和Cr(NO3)3（按各自占La,Al-SrTiO3质量比0.01wt%~0.5wt%）均匀球磨混合1~5小时，于200-800℃保温1-5小时，制得RhCrOx/La,Al-SrTiO3纳米颗粒；
（5）将步骤（4）合成的RhCrOx/La,Al-SrTiO3纳米颗粒分散水中，加入质量比为0.01wt%~0.5wt%的硝酸钴，300W氙灯光照1-12小时后，过滤洗涤并烘干，制得RhCrOx/La,Al-SrTiO3/CoOOH纳米复合光催化剂。
以上所述步骤中，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；步骤(3)中得到La,Al-SrTiO3纳米颗粒的尺寸为200-500纳米。
有益效果：本发明提供了一种双金属离子掺杂的纳米复合光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，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，具有更稳定的结构；本发明制备的RhCrOx/La,Al-SrTiO3/CoOOH材料能实现可见光下纯水分解，在光催化反应中具有很好的催化活性和稳定性；而且本发明制备工艺操作简单，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La,Al-SrTiO3材料的XRD图谱；
图2是本发明实施例1制得的La,Al-SrTiO3扫描电镜图；
图3是本发明实施例2制得的RhCrOx/La,Al-SrTiO3/CoOOH与单金属Al离子掺杂RhCrOx/Al-SrTiO3/CoOOH光催化水分解活性对比图。
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说明：
实施例1
一种双金属离子掺杂的纳米复合光催化剂的制备方法，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纳米催化剂材料，取0.5g La,Al-SrTiO3纳米颗粒，加入2.5mg的NaRhCl6和2.5mg的Cr(NO3)3，球磨混合1小时，于空气中600度煅烧2小时后，分散于100ml水中，加入2.5mgCo(NO3)2，300W氙灯光照8小时后，过滤洗涤并烘干，制得RhCrOx/La,Al-SrTiO3/CoOOH纳米复合光催化剂。
La,Al-SrTiO3纳米催化剂材料的XRD图如图1所示，其晶型保持了与SrTiO3相同的钙钛矿型，说明少量金属离子掺杂对其晶型改变影响不大。
扫描电镜图如图2所示，制得的La,Al-SrTiO3纳米颗粒尺寸在200-500纳米。
实施例2
一种双金属离子掺杂的纳米复合光催化剂的制备方法，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，取0.5g La,Al-SrTiO3纳米颗粒，加入1.0mg的NaRhCl6和2.5mg的Cr(NO3)3，球磨混合1小时，于空气中400度煅烧3小时后，分散于100ml水中，加入1.5mgCo(NO3)2，300W氙灯光照5小时后，过滤洗涤并烘干，制得RhCrOx/La,Al-SrTiO3/CoOOH纳米复合光催化剂。
将上述得到的RhCrOx/La,Al-SrTiO3/CoOOH纳米催化剂材料以及无La元素掺杂的RhCrOx/Al-SrTiO3/CoOOH催化剂用于光催化分解水，光催化水分解测试前，在紫外-可见全光谱照射纯水中测试其光催化水分解性能，催化剂用量为20mg，纯水200ml，光源为300W氙灯，如图3所示，RhCrOx/La,Al-SrTiO3/CoOOH纳米催化剂平均析氢速率为1056μmol/h/g，析氧速率为462μmol/h/g，氢氧比接近2：1，同条件下与RhCrOx/Al-SrTiO3/CoOOH催化剂相比，活性提升了1.4倍。
实施例3
一种双金属离子掺杂的纳米复合光催化剂的制备方法，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，取0.5g La,Al-SrTiO3纳米颗粒，加入1.5mg的NaRhCl6和0.5mg的Cr(NO3)3，球磨混合5小时，于空气中500度煅烧2小时后，分散于100ml水中，加入2.5mgCo(NO3)2，300W氙灯光照4小时后，过滤洗涤并烘干，制得RhCrOx/La,Al-SrTiO3/CoOOH纳米复合光催化剂。
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 (5)
1.一种双金属离子掺杂的纳米复合光催化剂，其特征在于，所述光催化剂为La,Al双金属离子共掺SrTiO3，并担载RhCrOx和CoOOH作为助催化剂；所述La摩尔占比为1％～10％，所述Al摩尔占比为1％～10％，所述RhCrOx和CoOOH的担载量为1.0wt％。
2.根据权利要求1所述的双金属离子掺杂的纳米复合光催化剂，其特征在于，所述La和Al为等摩尔比。
3.一种双金属离子掺杂的纳米复合光催化剂的制备方法，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)高温热处理后的样品洗涤除去多余的SrCl2，干燥后得到La,Al-SrTiO3纳米颗粒；
(4)将步骤(3)合成的La,Al-SrTiO3纳米颗粒与一定量的NaRhCl6和Cr(NO3)3,按各自占La,Al-SrTiO3质量比0.01wt％～0.5wt％均匀球磨混合1～5小时，于200-800℃保温1-5小时，制得RhCrOx/La,Al-SrTiO3纳米颗粒；
(5)将步骤(4)合成的RhCrOx/La,Al-SrTiO3纳米颗粒分散于水中，加入质量比为0.01wt％～0.5wt％的硝酸钴，300W氙灯光照1-12小时后，过滤洗涤并烘干，制得RhCrOx/La,Al-SrTiO3/CoOOH纳米复合光催化剂。
4.根据权利要求3所述的双金属离子掺杂的纳米复合光催化剂的制备方法，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。
5.根据权利要求3所述的双金属离子掺杂的纳米复合光催化剂的制备方法，其特征在于，步骤(3)中得到La,Al-SrTiO3纳米颗粒的尺寸为200-500纳米。
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