CN117070217A - 一种2d mol钝化无铅铋基混合卤化钙钛矿纳米点及其制备方法和应用 - Google Patents
一种2d mol钝化无铅铋基混合卤化钙钛矿纳米点及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种2D MOL钝化无铅铋基混合卤化钙钛矿纳米点及其制备方法和应用，由CSBB通过界面化学键分散在2D MOL的ZrTATB上合成，其分子式为CSBB‑X‑ZrTATB，其中X为CSBB的质量分数，0﹤X﹤100％，CSBB为钙钛矿Cs3Bi2‑ xSbxBr9，0﹤x≤0.4。本发明通过溶剂热合成2D MOL超薄纳米片，以溶剂热使2D MOL与钙钛矿前驱体溶液充分配位，反溶剂再结晶，制得CSBB‑X‑ZrTATB，具有优异的光催化C(sp3)‑H键活化反应活性和稳定性。
Description
技术领域
本发明涉及纳米材料制备和光催化技术领域，具体涉及一种2D MOL钝化无铅铋基混合卤化钙钛矿纳米点及其制备方法和在光催化C(sp3)-H键活化中的应用。
背景技术
通过选择性氧化活化饱和C-H键制备高附加值含氧化合物是合成化学中的一个具有挑战性的课题。传统的热催化活化通常受到苛刻的反应条件限制，例如高温、高压和使用高腐蚀性试剂。在这样苛刻的反应条件下由于部分氧化产物比相应的碳氢化合物更具反应活性，它们很容易被过度氧化成酸或二氧化碳，导致选择性降低。相比之下，具有活性自由基的光催化方法有望改变活化途径，降低活化势垒，最终在绿色温和条件下实现C(sp3)-H键活化。无铅卤化物钙钛矿在芳香烃的光催化转化方面显示出巨大的潜力。与大多数无铅碘卤化物钙钛矿相比，价带位置相对正的无铅溴化物和氯化物钙钛矿具有更强的氧化能力，更有利于光催化C(sp3)-H键活化。作为一种低毒稳定的光催化材料，Cs3Bi2Br9近年来逐渐受到研究人员的关注，然而，由于光生载流子的快速复合且Cs3Bi2Br9在环境下不稳定。另外，Cs3Bi2Br9催化过程中产生的氧活性物种为超氧自由基，导致产物容易过渡氧化，不利于产物选择性的提升，其光催化活性需要进一步优化。掺杂和异质结的设计能实现高效的电子传输，提高钙钛矿的活性性和稳定性。但上述两种方法仍然存在问题，其中掺杂只适用于少量元素的制备，普适性较差。另外，通过自组装形成的异质结的稳定性较差。
发明内容
为了解决现有技术中存在的问题，本发明的目的是在于提供了一种2D MOL钝化无铅铋基混合卤化钙钛矿纳米点及其制备方法和应用，通过溶剂热合成2DMOL超薄纳米片，以溶剂热使2D MOL与钙钛矿前驱体溶液充分配位，反溶剂再结晶，制得CSBB-X-ZrTATB，具有优异的光催化C(sp3)-H键活化反应活性和稳定性。
为了实现上述技术目的，本发明采用如下技术方案：
一种2D MOL钝化无铅铋基混合卤化钙钛矿纳米点，由CSBB通过界面化学键分散在2D MOL的ZrTATB上而成，其分子式为CSBB-X-ZrTATB，其中X为CSBB的质量分数，0﹤X﹤100％，CSBB为钙钛矿Cs3Bi2-xSbxBr9，0﹤x≤0.4。
作为优选，所述分子式中，25％≤X≤90％；进一步优选为65％≤X≤85％；更进一步优选为70％≤X≤80％。
本发明还提供了上述2D MOL钝化无铅铋基混合卤化钙钛矿纳米点的制备方法，包括如下步骤：
(1)通过溶剂热法制备2D MOL ZrTATB超薄纳米片；
(2)将步骤(1)得到的2D MOL ZrTATB超声分散在DMSO中，再加入CsBr、BiBr3和SbBr3，通过溶剂热法进行预配位，得到前驱体溶液；
(3)将步骤(2)中获得的前驱体溶液加入到异丙醇中，通过反溶剂法结晶得到CSBB-X-ZrTATB。
作为优选，步骤(1)中，2D MOL ZrTATB超薄纳米片的制备过程为：先将ZrOCl2·8H2O、DMF和冰醋酸充分混匀，于85℃反应2h；再加入H3TATB，升温至120℃继续反应12h即得到2D MOL ZrTATB超薄纳米片。
作为优选，步骤(2)中，所述BiBr3和SbBr3的摩尔比为1.7：0.3～1.9：0.1，CsBr在DMSO中的浓度为10～20mM。
作为优选，步骤(2)中，所述溶剂热的反应条件为：温度50～70℃，时间8～16h。
作为优选，步骤(3)中，所述前驱体溶液和异丙醇的体积比为1：20～30。
作为优选，步骤(3)中，所述反溶剂法结晶的时间为0.5～5min。
本发明还提供了上述2D MOL钝化无铅铋基混合卤化钙钛矿纳米点的应用，将其用于光催化C(sp3)-H键活化反应。
本发明采用2D MOL超薄片钝化少量Sb掺杂的钙钛矿，通过溶剂热与反溶剂再结晶法可控合成钙钛矿纳米点。本发明通过以2D MOL中垂直Zr-O簇的甲酸基团锚定CSBB中Bi+3，可控的合成钙钛矿纳米点，一方面界面化学键的作用实现了钙钛矿纳米点的可控合成，提高了催化剂的稳定性与活性位点的暴露，另一方面界面化学键构建的离子通道促进光生空穴的分离效率。同时，2D MOL与钙钛矿的作用使活性氧物种转变为单线态氧提升了氧化产物的选择性。
与现有技术相比，本发明的优点：
本发明以简单的溶剂热预配位与反溶剂再结晶法结合制备了CSBB-X-ZrTATB光催化剂，通过形成界面化学键实现钙钛矿纳米点的可控制备，提升了活性位点的暴露，离子通道促进了光生载流子的分离效率。2D MOL的疏水性降低了钙钛矿对水的浸润性，提高了钙钛矿材料的稳定性。2D MOL与钙钛矿的作用使活性氧物种转变为单线态氧提升了氧化产物的选择性。
附图说明
图1为实施例1(c)、对比例1(b)和对比例2(a)制得的样品的SEM图。
图2为实施例1(c-g)、对比例1(b)和对比例2(a)制得的样品的TEM图。
图3为实施例1、对比例1和对比例2制得的样品的XRD图。
图4为实施例1-4和对比例1-3制得的样品催化性能对比图。
图5为实施例1、对比例1和对比例2制得的样品的光催化甲苯氧化中自由基捕获测试和原位ESR表征图。
图6为实施例1(b)和对比例2(a)制得的样品的接触角测试图。
具体实施方式
下面结合实施例对本发明做进一步详细说明，但本发明的保护范围并不局限于这些实施例。
对比例1
以溶剂热合成2D MOL ZrTATB超薄纳米片，在20mL带盖玻璃瓶中依次加入190mgZrOCl2·8H2O，6mL DMF，4mL冰醋酸，混合均匀后在85℃烘箱中反应2h。再加入44mg H3TATB，升温至120℃继续反应12h。离心收集固体，依次以DMF，丙酮洗涤三次。固体材料在60℃真空烘箱中干燥12h，得2D MOL ZrTATB超薄纳米片。
实施例1
2D MOL ZrTATB超薄纳米片的制备同对比例1。
在含有0.45mmol CsBr、0.075mmol SbBr3和0.225mmol BiBr3的30mL DMSO前驱体溶液中加入50mg ZrTATB，超声分散2h。60℃的油浴锅中搅拌12h。冷却至室温，在剧烈搅拌下，将2mL前驱体溶液加入到30mL异丙醇中，快速搅1min。用氯仿洗涤三次，在60℃真空烘箱中干燥12小时，得到黄色CSBB-75-ZrTATB纳米片。
实施例2
2D MOL ZrTATB超薄纳米片的制备同对比例1。
在含有0.45mmol CsBr、0.075mmol SbBr3和0.225mmol BiBr3的30mL DMSO前驱体溶液中加入450mg ZrTATB，超声分散2h。60℃的油浴锅中搅拌12h。冷却至室温，在剧烈搅拌下，将2mL前驱体溶液加入到30mL异丙醇中，快速搅1min。用氯仿洗涤三次，在60℃真空烘箱中干燥12h，得到黄色CSBB-25-ZrTATB纳米片。
实施例3
2D MOL ZrTATB超薄纳米片的制备同对比例1。
在含有0.45mmol CsBr、0.075mmol SbBr3和0.225mmol BiBr3的30mL DMSO前驱体溶液中加入150mg ZrTATB，超声分散2h。60℃的油浴锅中搅拌12h。冷却至室温，在剧烈搅拌下，将2mL前驱体溶液加入到30mL异丙醇中，快速搅1min。用氯仿洗涤三次，在60℃真空烘箱中干燥12h，得到黄色CSBB-50-ZrTATB纳米片。
实施例4
2D MOL ZrTATB超薄纳米片的制备同对比例1。
在含有0.45mmol CsBr、0.075mmol SbBr3和0.225mmol BiBr3的30mL DMSO前驱体溶液中加入17mg ZrTATB，超声分散2h。60℃的油浴锅中搅拌12h。冷却至室温，在剧烈搅拌下，将2mL前驱体溶液加入到30mL异丙醇中，快速搅1min。用氯仿洗涤三次，在60℃真空烘箱中干燥12h，得到黄色CSBB-90-ZrTATB纳米片。
对比例2
将0.45mmol CsBr、0.075mmol SbBr3和0.225mmol BiBr3溶于30mL的DMSO中，得到前驱体溶液。然后，在剧烈搅拌下，将2mL前驱体溶液加入到50mL异丙醇中，快速搅1min。用氯仿洗涤三次，在60℃真空烘箱中干燥12h，得到黄色Cs3Bi1.8Sb0.2Br9纳米颗粒。
对比例3
2D MOL ZrTATB超薄纳米片的制备同对比例1。
Cs3Bi1.8Sb0.2Br9纳米颗粒的制备同对比例2。
将2D MOL ZrTATB超薄纳米片和Cs3Bi1.8Sb0.2Br9纳米颗粒按照质量比为25：75直接进行物理混合，得到CSBB-75-ZrTATB-Mix。
以光催化C(sp3)-H键活化为模型反应考察所制备的样品的催化活性：
首先将5mg催化剂分散到2mL的反应底物中，以液氮冻融三次，填充氧气球(保持压力1atm)，混合物在黑暗中磁力搅拌30min将氧气引入反应混合物的底部，建立吸附-解吸平衡。光源采用300W氙灯配有λ≥400nm滤光片，光照2h。以气相色谱仪通过内标法定量分析。在岛津GC2010Plus色谱仪上定量，配备FID检测器和WAX毛细管柱(30m×0.25mm×0.25μm)。
实施例1-4和对比例1-2制得的样品的光催化甲苯氧化反应的结果如表1所示：
表1实施例1-4和对比例1-2制得的样品的光催化甲苯氧化反应结果
由表1可知，单一的ZrTATB并没有催化活性，单一的Cs3Bi1.8Sb0.2Br9的苯甲醛和苯甲醇的生成速率分别仅为3.373mmol g-1h-1和0.437mmol g-1h-1，而将CSBB与MOL原位复合后，明显提升了催化活性，特别是CSBB-75-ZrTATB的苯甲醛和苯甲醇的生成速率分别为14.481mmol g-1h-1和2.006mmol g-1h-1，光催化效果最好。
表2实施例1和对比例3制得的样品的光催化甲苯氧化反应结果
由表2可知，通过界面化学键形成的CSBB-75-ZrTATB比简单的物理混合所得到CSBB-75-ZrTATB-Mix的甲苯转化的速率明显要高，CSBB-75-ZrTATB-Mix的苯甲醛和苯甲醇的生成速率分别为8.330mmol g-1h-1和1.214mmol g-1h-1。
以实施例1制得的CSBB-75-ZrTATB，测试带有其他取代基的甲苯衍生物，其结果如表3所示：
表3实施例1制得的样品的光催化甲苯衍生物氧化反应结果
注：a反应条件：2mL底物，5mg CSBB-75ZrTATB作为光催化剂，λ≥400nm，O2 1atm，反应时间3h。b将固体对硝基甲苯(1.29g，相对密度1.29g mL-1)溶解在2.5mL乙腈中反应。
如图1的SEM所示，图1(a)Cs3Bi1.8Sb0.2Br9以大的块状的形式存在。图1(b)ZrTATB为超薄的纳米片，厚度为4nm左右，图1(c)是CSBB-75-ZrTATB与图1(b)的形状类似，均为超薄的纳米片，且能看到少量的钙钛矿且尺寸较小，说明2D MOL与钙钛矿结合后有效的钝化钙钛矿，且避免了钙钛矿堆积成大的块状。
如图2的TEM所示，(a)Cs3Bi1.8Sb0.2Br9也是大的块状形式存在。(b)ZrTATB为超薄的纳米片，(c)CSBB-75-ZrTATB很难看到钙钛矿材料，通过对其表面进行局部放大，出现了钙钛矿纳米点(e)，说明通过界面化学键的作用，可以可控的在2D MOL上制备钙钛矿纳米点，高倍透射电镜显示钙钛矿为主要为(112)(003)(201)晶面(f)，进一步证实了钙钛矿在MOL上纳米点的形式存在。元素分布证实元素均匀分布在所选的区域范围内(g)。
如图3XRD表征所示，通过与ZrTATB的模拟图对比证实了ZrTATB的成功。CSBB(Cs3Bi1.8Sb0.2Br9)与CSB(Cs3Sb2Br9)和CBB(Cs3Bi2Br9)的标准卡片对比也证实了CSBB的成功合成，进一步证实了CSBB-75-ZrTATB的成功合成。
如图4的性能对比测试所示，在CSBB含量在75wt％的催化性能最佳，纯的ZrTATB没有催化活性，CSBB的催化活性较低，甲苯的转化速率仅为3.810mmol h-1g-1,与2D MOL结合后的活性均比单一的CSBB活性高，CSBB-75-ZrTATB的甲苯转化速率高达16.487mmol h-1g-1，可能的原因是2DMOL表面的甲酸基团与钙钛矿形成较强的离子键稳定了钙钛矿，构建了离子通道加速了光生电子空穴的生成，另一方面2D MOL的钝化作用减小了钙钛矿的尺寸，使更多的活性位点暴露。2D MOL的疏水性降低了钙钛矿的水的浸润性，增强了钙钛光的稳定性(图6)。循环实验中催化剂循环六次后催化活性几乎没有下降，进一步证实了2D MOL通过界面化学键提升了钙钛矿的稳定性。
如图5所示，通过自由基捕获实现发现单线态氧为主要的氧活性物种(a)，而对CSBB进行自由基捕获表明主要氧活性种为超氧自由基，进一步以原位的ESR检测发现单一的CSBB(c)和ZrTATB(b)均不能产生单线态氧，但是两者通过界面化学键结合后产生了单线态氧(d)。
Claims (10)
1.一种2D MOL钝化无铅铋基混合卤化钙钛矿纳米点，其特征在于：由CSBB通过界面化学键分散在2D MOL的ZrTATB上而成，其分子式为CSBB-X-ZrTATB，其中X为CSBB的质量分数，0﹤X﹤100％，CSBB为钙钛矿Cs3Bi2-xSbxBr9，0﹤x≤0.4。
2.根据权利要求1所述的2D MOL钝化无铅铋基混合卤化钙钛矿纳米点，其特征在于：所述分子式中，25％≤X≤90％。
3.根据权利要求2所述的2D MOL钝化无铅铋基混合卤化钙钛矿纳米点，其特征在于：所述分子式中，65％≤X≤85％。
4.权利要求1-3任一项所述的2D MOL钝化无铅铋基混合卤化钙钛矿纳米点的制备方法，其特征在于：包括如下步骤：
(1)通过溶剂热法制备2D MOL ZrTATB超薄纳米片；
(2)将步骤(1)得到的2D MOL ZrTATB超声分散在DMSO中，再加入CsBr、BiBr3和SbBr3，通过溶剂热法进行预配位，得到前驱体溶液；
(3)将步骤(2)中获得的前驱体溶液加入到异丙醇中，通过反溶剂法结晶得到CSBB-X-ZrTATB。
5.根据权利要求4所述的制备方法，其特征在于：步骤(1)中，2D MOL ZrTATB超薄纳米片的制备过程为：先将ZrOCl2·8H2O、DMF和冰醋酸充分混匀，于85℃反应2h；再加入H3TATB，升温至120℃继续反应12h即得到2D MOL ZrTATB超薄纳米片。
6.根据权利要求4所述的制备方法，其特征在于：步骤(2)中，所述BiBr3和SbBr3的摩尔比为1.7：0.3～1.9：0.1，CsBr在DMSO中的浓度为10～20mM。
7.根据权利要求4所述的制备方法，其特征在于：步骤(2)中，所述溶剂热的反应条件为：温度50～70℃，时间8～16h。
8.根据权利要求4所述的制备方法，其特征在于：步骤(3)中，所述前驱体溶液和异丙醇的体积比为1：20～30。
9.根据权利要求4所述的制备方法，其特征在于：步骤(3)中，所述反溶剂法结晶的时间为0.5～5min。
10.权利要求1-3任一项所述的2D MOL钝化无铅铋基混合卤化钙钛矿纳米点或权利要求4-9任一项所述的制备方法制得的2D MOL钝化无铅铋基混合卤化钙钛矿纳米点的应用，其特征在于：将其用于光催化C(sp3)-H键活化反应。
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