CN113289689B - Z型异质结Co9S8/NH2-UiO-66复合材料的制备方法及其在光催化中的应用 - Google Patents
Z型异质结Co9S8/NH2-UiO-66复合材料的制备方法及其在光催化中的应用 Download PDFInfo
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Abstract
本发明涉及Z型异质结Co9S8/NH2‑UiO‑66复合材料的制备方法及其在光催化中的应用。所述的Z型异质结Co9S8/NH2‑UiO‑66复合材料是将Co9S8纳米粒子负载到金属有机骨架NH2‑UiO‑66表面，形成异质结。制备方法如下：采用水热法分别合成NH2‑UiO‑66和Co9S8纳米粒子；将NH2‑UiO‑66和Co9S8纳米粒子分散在乙醇溶液中超声作用，然后蒸发乙醇溶剂诱导Co9S8纳米粒子在NH2‑UiO‑66上复合，真空干燥得目标产物。本发明提供的Co9S8/NH2‑UiO‑66复合材料对Biginelli反应展示出良好的催化性能。
Description
技术领域
本发明属于催化技术领域，具体涉及一种金属有机骨架NH2-UiO-66(Zr)负载Co9S8纳米粒子形成的Z型异质结复合材料的制备方法以及在无溶剂、无助催化剂的温和条件下高效催化Biginelli反应的应用。
背景技术
半导体在光催化反应中处于核心位置，它能吸收太阳能直接转化为氢气、甲烷、甲酸等太阳能燃料，从而缓解当代社会的能源问题。但半导体的电子空穴复合速度快，光利用率低，光催化反应的光转换效率很低，研究者采用半导体复合的方法使光催化剂的活性得到了提高。金属有机骨架(MOFs)材料具有高比表面积、低密度、高孔隙率、可调的孔径及多功能活性位点等优点，被广泛应用于光催化领域。将MOFs与半导体复合形成Z型异质结光催化复合材料可以降低电子空穴复合速率，提高复合材料的氧化还原性能，被认为是提高光催化活性的一种有效途径。
3,4-二氢锥体酮类(3,4-DHPM)是一种广泛用作抗肿瘤剂、镇痛剂和抗癌药物的喹唑啉酮衍生物。由于其重要的特性，合成3,4-DHPM衍生物是非常重要的。多组分Biginelli反应提供了一种直接而简单的方法，该反应使用的原料容易获得，即醛、活性亚甲基化合物和 (硫)脲，通过酸催化一锅合成3,4-DHPM。在过去的二十年中，DHPM由于其广泛的药理活性和多种天然产物的存在而激发了人们的兴趣。在材料化学中，二氢锥体酮类在聚合物，粘合剂，织物染料等材料的开发中越来越多地获得应用。鉴于Biginelli反应的简便性，其在各个领域的应用有广泛的前景。
然而，多组分Biginelli反应使用昂贵的有毒强酸、低产量和长时间的加热等问题仍然是比吉内利合成的不理想的限制。因此，设计和开发复合材料作为光催化剂来催化诱导3,4- DHPM衍生物的合成将会获得很好的研究成果。
发明内容
本发明的目的是通过溶剂热法将NH2-UiO-66和纳米粒子Co9S8复合合成Co9S8/NH2-UiO-66复合材料，并研究其作为光催化剂，对光催化Biginelli反应的催化性能。
本发明采用的技术方案为：Z型异质结Co9S8/NH2-UiO-66复合材料，是将Co9S8纳米粒子负载到金属有机骨架NH2-UiO-66表面，形成的Z型异质结。
优选的，上述的Z型异质结Co9S8/NH2-UiO-66复合材料，按质量百分比，含有5-20％的Co9S8。
一种Z型异质结Co9S8/NH2-UiO-66复合材料的制备方法，制备方法包括如下步骤：
1)将ZrCl4和2-氨基对苯二甲酸(NH2-BDC)溶于DMF中，搅拌后加入冰乙酸溶液，混合均匀，所得混合物在120℃油浴中持续加热搅拌12h，离心，所得固体洗涤、干燥，得 NH2-UiO-66；
2)将CoCl2·6H2O溶解于去离子水中，搅拌后，缓慢加入Na2S·9H2O溶液，连续搅拌30min后，转移到反应釜中120℃加热20h，离心，所得固体洗涤、干燥，得Co9S8纳米粒子；
3)将NH2-UiO-66和Co9S8纳米粒子分散在乙醇溶液中，超声30min，然后将所得混合物加热挥发乙醇溶剂，诱导Co9S8纳米粒子在NH2-UiO-66上复合，干燥，得目标产物Z型异质结Co9S8/NH2-UiO-66复合材料。
优选的，上述的制备方法，步骤1)中，按摩尔比，ZrCl4:2-氨基对苯二甲酸＝0.2-0.3: 0.4-0.5。
优选的，上述的制备方法，步骤2)中，按摩尔比，CoCl2·6H2O:Na2S·9H2O＝0.1-0.2: 1-2。
优选的，上述的制备方法，步骤3)中，按质量比，NH2-UiO-66:Co9S8纳米粒子＝1:0.05-0.2。
本发明提供的Z型异质结Co9S8/NH2-UiO-66复合材料在光催化Biginelli反应中的应用。
进一步的，方法如下：取苯甲醛、乙酰乙酸乙酯、尿素和催化剂于试管中，氮气保护下，于70℃反应10min；所述催化剂是Z型异质结Co9S8/NH2-UiO-66复合材料。
本发明的有益效果是：
1、本发明提供的Co9S8/NH2-UiO-66复合材料，具有Z型异质结结构，能够有效地抑制电子空穴的复合，使载流子能很快的转移，提高了电荷转移效率，使催化反应速率加快。
2、本发明提供的Co9S8/NH2-UiO-66复合材料，具有较大的比表面积，可以有效地捕获光能转移电子，使催化反应速率加快。
3、本发明提供的Co9S8/NH2-UiO-66复合材料，形成Z型异质结构，提高了氧化还原能力，能加速光催化反应的进行。
4、本发明提供的Co9S8/NH2-UiO-66复合材料，对Biginelli反应展示出良好的催化性能。
5、本发明提供的Co9S8/NH2-UiO-66复合材料，合成方法简单，原材料廉价易得，具有应用前景。
附图说明
图1是实施例1制备的NH2-UiO-66和模拟的NH2-UiO-66的PXRD谱图。
图2是Co9S8、NH2-UiO-66和Co9S8/NH2-UiO-66的PXRD谱图。
图3是NH2-UiO-66(a)，Co9S8(b)和Co9S8/NH2-UiO-66(c)的SEM图。
图4是NH2-UiO-66，Co9S8和Co9S8/NH2-UiO-66的光电流响应图。
图5是NH2-UiO-66、Co9S8和Co9S8/NH2-UiO-66的N2吸附等温线。
图6是Co9S8/NH2-UiO-66的能级及其电子传输图。
具体实施方式
实施例1 Z型异质结Co9S8/NH2-UiO-66复合材料
(一)制备方法如下：
(1)将ZrCl4(61.2mg，0.26mmol)和2-氨基对苯二甲酸(87mg，0.48mmol)溶于 60mLDMF中，混合搅拌5min后，向其中加入7.2mL冰乙酸溶液，混合均匀。所得混合物在120℃油浴中持续加热搅拌12h，产生黄色固体，离心、洗涤、干燥，得产物NH2- UiO-66。
(2)将CoCl2·6H2O(34.04mg，0.14mmol)溶解于15mL去离子水中，搅拌后，将 10mLNa2S·9H2O水溶液(含Na2S·9H2O 171.80mg，1.79mmol)缓慢加入到CoCl2·6H2O水溶液中，Co/S摩尔比为1:5。随后将混合溶液连续搅拌30min。转移到50mL反应釜中 120℃加热，20h，得到黑色沉淀，离心、洗涤、干燥，得产物Co9S8。
(3)将50mg NH2-UiO-66和7.5mg Co9S8纳米粒子分散在25mL乙醇溶液中，超声作用30min，然后将所得混合物在70℃下搅拌约2h，蒸发乙醇溶剂，诱导Co9S8纳米粒子在 NH2-UiO-66上复合。最后在60℃真空干燥箱中干燥，得目标产物Co9S8/NH2-UiO-66复合材料，标记为15％Co9S8/NH2-UiO-66。
(二)检测
图1和图2是本发明合成的NH2-UiO-66以及Z型异质结Co9S8/NH2-UiO-66复合材料的 PXRD图。由图1可见，所合成的NH2-UiO-66中的衍射峰与模拟PXRD峰相吻合，结果证实NH2-UiO-66成功合成。由图2可见，纯Co9S8只显示了两个非常弱和宽的特征衍射峰，这表明了非晶形Co9S8的存在；Co9S8/NH2-UiO-66的XRD特征衍生峰中有NH2-UiO-66的和Co9S8的特征峰，由此可以证实NH2-UiO-66和Co9S8已成功复合。
图3是NH2-UiO-66(a)，Co9S8(b)和Co9S8/NH2-UiO-66(c)的SEM图。由图3扫描电镜也可以看到NH2-UiO-66和纳米粒子Co9S8的形貌基本保持不变并且球形Co9S8纳米粒子附着在NH2-UiO-66八面体的表面上，说明了纳米粒子Co9S8与NH2-UiO-66已成功复合，形成了Co9S8/NH2-UiO-66复合材料。
图4是本发明合成的Z型异质结Co9S8/NH2-UiO-66复合材料的光电流响应图。如图4所示，Co9S8/NH2-UiO-66比Co9S8和NH2-UiO-66表现出最高的光电流密度，进一步表明，Co9S8/NH2-UiO-66Z型异质结的形成有助于分离光产生的电子空穴对。
图5是本发明合成的Z型异质结Co9S8/NH2-UiO-66复合材料的N2吸附等温线图。NH2-UiO-66具有高Langmuir比表面积。Co9S8比表面积为22m2g-1，平均孔直径为23.9nm，如图5所示，具有介孔结构。Co9S8/NH2-UiO-66复合材料具有Ⅱ型等温线，最大程度上保留了 NH2-UiO-66较大的比表面积，比表面积的轻微下降可能是因为纳米粒子Co9S8的覆盖造成的。
如图6所示，通过实验与计算，计算得到Co9S8和NH2-UiO-66的带隙能级(Eg)和导带(CB)边缘位置。在可见光光照射下NH2-UiO-66和Co9S8价带上的电子发生激发由价带转移到导带上，电子在纳米粒子Co9S8的导带上富集，空穴在NH2-UiO-66的价带上富集，复合材料表现出一种Z型异质结结构。
实施例2 Z型异质结Co9S8/NH2-UiO-66复合材料对Biginelli反应的催化功能
(一)Co9S8纳米粒子的添加量对催化Biginelli反应的影响
取50mg NH2-UiO-66，分别加入2.5mg、5.0mg、10.0mg Co9S8纳米粒子分散在25mL乙醇溶液中，超声作用30min，然后将所得混合物在70℃下搅拌约2h，蒸发乙醇溶剂，诱导Co9S8纳米粒子在NH2-UiO-66上复合。最后在60℃真空干燥箱中干燥，得目标产物 Co9S8/NH2-UiO-66复合材料，分别标记为5％Co9S8/NH2-UiO-66、10％Co9S8/NH2-UiO-66、 20％Co9S8/NH2-UiO-66。
方法：取20mg不同Co9S8负载量的Z型异质结Co9S8/NH2-UiO-66复合材料、1mmol 苯甲醛、1mmol乙酰乙酸乙酯和1.5mmol尿素于10mL的反应管中，氮气保护下，于70℃反应10min。实验结果称重，用核磁氢谱检测。结果如表1。
反应式如下：
表1
| 催化剂 | m(NH<sub>2</sub>-UiO-66)(mg) | m(Co<sub>9</sub>S<sub>8</sub>)(mg) | 催化效率(％) |
| 5％Co<sub>9</sub>S<sub>8</sub>/NH<sub>2</sub>-UiO-66 | 50 | 2.5 | 80.7 |
| 10％Co<sub>9</sub>S<sub>8</sub>/NH<sub>2</sub>-UiO-66 | 50 | 5.0 | 82.3 |
| 15％Co<sub>9</sub>S<sub>8</sub>/NH<sub>2</sub>-UiO-66 | 50 | 7.5 | 89.4 |
| 20％Co<sub>9</sub>S<sub>8</sub>/NH<sub>2</sub>-UiO-66 | 50 | 10.0 | 83.5 |
由表1可见，用该Z型异质结Co9S8/NH2-UiO-66复合材料对Biginelli反应进行催化，随着Co9S8加入量的增加，反应的产率逐渐增加，当添加到15％含量时，催化效率最高，可达89.4％。
Claims (5)
1.Z型异质结Co9S8/NH2-UiO-66复合材料在光催化Biginelli反应中的应用，其特征在于，所述Z型异质结Co9S8/NH2-UiO-66复合材料，是将Co9S8纳米粒子负载到金属有机骨架NH2-UiO-66表面，形成的Z型异质结；按质量百分比，含有5-20%的Co9S8，制备方法包括如下步骤：
1）将ZrCl4和2-氨基对苯二甲酸溶于DMF中，搅拌后加入冰乙酸溶液，混合均匀，所得混合物在120℃ 油浴中持续加热搅拌12 h，离心，所得固体洗涤、干燥，得NH2-UiO-66；
2）将CoCl2•6H2O溶解于去离子水中，搅拌后，缓慢加入Na2S•9H2O溶液，连续搅拌30 min后，转移到反应釜中120℃ 加热20 h，离心，所得固体洗涤、干燥，得Co9S8纳米粒子；
3）将NH2-UiO-66和Co9S8纳米粒子分散在乙醇溶液中，超声30 min，然后将所得混合物加热挥发乙醇溶剂，诱导Co9S8纳米粒子在NH2-UiO-66上复合，干燥，得目标产物Z型异质结Co9S8/NH2-UiO-66复合材料。
2.根据权利要求1所述的应用，其特征在于，步骤1）中，按摩尔比，ZrCl4: 2-氨基对苯二甲酸=0.2-0.3 : 0.4-0.5。
3.根据权利要求1所述的应用，其特征在于，步骤2）中，按摩尔比，CoCl2•6H2O : Na2S•9H2O=0.1-0.2 : 1-2。
4.根据权利要求1所述的应用，其特征在于，步骤3）中，按质量比，NH2-UiO-66 : Co9S8纳米粒子=1 : 0.05-0.2。
5.根据权利要求1所述的应用，其特征在于，方法如下：取苯甲醛、乙酰乙酸乙酯、尿素和催化剂于试管中，氮气保护下，于70℃ 反应10 min；所述催化剂是权利要求1所述的Z型异质结Co9S8/NH2-UiO-66复合材料。
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