CN113718338B - 一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用 - Google Patents
一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用，该炔银簇材料的化学式为：C133H165Ag18Cl3F6O14S8，属于单斜晶系，空间群为C2/m，晶胞参数为α＝90°，β＝119.703(3)°，γ＝90°，该炔银簇材料不仅具有良好的光电流响应，而且还具有荧光传感器性质，可广泛用于光电催化领域和荧光传感器领域。
Description
技术领域
本发明涉及无机纳米材料，尤其涉及一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用。
背景技术
金属纳米簇合物是一种纳米级尺度的超细颗粒，它们的性质与宏观金属的性质完全不同。由过渡金属铜、银和金组成的第11族金属除了具有有趣的电子结构还有丰富多样的几何结构，其中银纳米簇合物的研究最为广泛。
由配体保护的原子精度高的银纳米团簇因其特殊的性能和广泛的应用而在材料领域引起了广泛的关注。在不同的有机配体的保护下，它们的结构有明显的不同，这说明配体的配位性、体积性和电子性质对银纳米簇合物的结构、稳定性和性质都有重要影响。
炔基、硫醇、有机膦配体已被广泛用于与银离子配位，从而形成各种结构的银纳米簇合物。利用传统配体以外的有机配体(特别是大环配体)制备银纳米簇合物一直是一个巨大的挑战。杯芳烃是苯酚单元之间通过亚甲基桥接而成的一类环状低聚物，被认为是继冠醚和环糊精之后新一代大环化合物的代表，也被称为第三代“超分子宿主化合物”。硫杂杯[4]芳烃是其众多衍生物中的一种，它具有与杯芳烃相同的结构和形状。其桥接硫原子有一个孤对电子和一个三维空轨道，孤电子对可以参与金属阳离子的配位形成稳定的化合物。
一个硫杂杯[4]芳烃分子可以同时结合和稳定四个3d或4f金属离子，硫杂杯[4]芳烃的多齿配位点有利于形成更高核银纳米团簇。一方面，高核银纳米簇具有良好的光致电子/空穴对的产生和分离效率以及光化学稳定性，在光电化学方面具有潜在的应用前景；另一方面，高核银纳米簇对不同极性的有机溶剂显示出良好的荧光传感性质，在荧光传感器方面也有着潜在的应用前景。因此，开发新型的功能性高核银簇材料，成为研究方向之一。
发明内容
本发明的目的是提供一种硫杂杯[4]芳烃保护的炔银簇材料及其制备方法和应用，该材料具有良好的光电流响应特性和荧光传感性质。
为了解决现有技术存在的问题，本发明采用的技术方案如下：
一种硫杂杯[4]芳烃保护的炔银簇材料，所述炔银簇材料的化学式为：C133H165Ag18Cl3F6O14S8。
进一步地，所述炔银簇材料属于单斜晶系，空间群为C2/m，晶胞参数为α＝90°，β＝119.703(3)°，γ＝90°，
一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，包括以下步骤：
①将叔丁基炔银配体、CF3COOAg以及对叔丁基硫杂杯[4]芳烃溶解在溶剂中，混合均匀后得到悬浊液；
②迅速加入新制的NaBH4乙醇溶液后，常温搅拌10分钟，然后在超声波振荡下搅拌30分钟；
③然后转移至25mL聚四氟乙烯内衬的不锈钢高压反应釜中，将高压反应釜放入电热鼓风干燥箱内升温至65℃后恒温24小时，反应结束后冷却至室温，得到混合溶液；
④将混合溶液过滤得到滤液；
⑤将滤液挥发，得到块状晶体。
其中，所述叔丁基炔银配体、CF3COOAg、对叔丁基硫杂杯[4]芳烃的摩尔比为12.5:5:1。
其中，步骤①中所述溶剂是由甲醇、三氯甲烷以及甲苯组成的混合溶剂，所述甲醇、三氯甲烷、甲苯的体积比为3:3:1。
其中，所述步骤③制备的混合溶液的pH值为6.0-6.5。
其中，所述步骤②中NaBH4乙醇溶液的浓度为1mg/mL，所述NaBH4乙醇溶液的体积是所述甲苯体积的一半。
一种硫杂杯[4]芳烃保护的炔银簇材料作为催化剂在光电催化领域的应用。
一种硫杂杯[4]芳烃保护的炔银簇材料在荧光传感器上的应用。
本发明所具有的优点和有益效果是：
本发明一种硫杂杯[4]芳烃保护的炔银簇材料，是采用叔丁基炔银配体和对叔丁基硫杂杯[4]芳烃配体共同合成的一个高核银簇，具有良好的光电流响应特性和荧光传感性能，可广泛用于光电催化和荧光传感器领域。
附图说明
下面结合附图对本发明作进一步详述：
图1为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的晶体结构图；
图2为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的X-射线光电子能谱图；
图3为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的粉末X-射线多晶衍射曲线；
图4为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的红外光谱图；
图5为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的质谱图；
图6为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的固态紫外-可见吸收光谱图；
图7为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的固态漫反射光谱图；
图8为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的光电流密度图；
图9为本发明一种硫杂杯[4]芳烃保护的炔银簇材料的固态发射光谱图；
图10为本发明一种硫杂杯[4]芳烃保护的炔银簇材料在不同溶剂中的发射光谱图；
图11为本发明一种硫杂杯[4]芳烃保护的炔银簇材料在不同溶剂中的发射峰强度对应的柱状图。
具体实施方式
下面结合实施例对本发明进行进一步的解释，但是并不用于限制本发明的保护范围。
本发明一种硫杂杯[4]芳烃保护的炔银簇材料，不仅具有良好的光电流响应特性，而且还具有良好的荧光传感性质，其化学式为：C133H165Ag18Cl3F6O14S8，所述炔银簇材料属于单斜晶系，空间群为C2/m，晶胞参数为 α＝90°，β＝119.703(3)°，γ＝90°，/>
一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，包括以下步骤：
①将叔丁基炔银配体(以下简写为[tBuC≡CAg]n，n代表叔丁基炔银为难溶物)、CF3COOAg以及对叔丁基硫杂杯[4]芳烃(以下简写为H4TC4A)溶解在由甲醇、三氯甲烷以及甲苯组成的溶剂中，混合均匀后得到浅黄色悬浊液。
②再迅速向该浅黄色悬浊液中加入新制的NaBH4乙醇溶液，得到棕黑色悬浊液，常温搅拌10分钟，然后在超声波振荡下搅拌30分钟；
③将棕黑色悬浊液转移至25mL聚四氟乙烯内衬的不锈钢高压反应釜中，放入电热鼓风干燥箱内升温至65℃后恒温24小时，反应结束后冷却至室温，得到淡黄色混合溶液，此淡黄色混合溶液pH值为6.0-6.5，其中，偏酸性条件下不易发生银镜反应，而且有利于Ag+聚集成核。
④将上述淡黄色混合溶液过滤，得到淡黄色透明滤液；
⑤将上述淡黄色透明滤液在室温下挥发，通常室温为25℃，2天后得到淡黄色的块状晶体，即产物。
其中，步骤①中[tBuC≡CAg]n、CF3COOAg、H4TC4A的摩尔比为12.5:5:1，溶剂中甲醇、三氯甲烷、甲苯的体积比为3:3:1。
对本发明一种硫杂杯[4]芳烃保护的炔银簇材料进行结构表征和性质研究。如图5所示，该炔银簇材料在三氯甲烷中的MALDI-TOF MS分析表明该炔银簇以[Ag9(TC4A)(tBuC≡C)4]2 2+的形式稳定的存在。如图6、7所示，测试了该炔银簇材料的固态紫外-可见吸收光谱和漫反射光谱；用Kubelka-Munk(KM)方法从漫反射光谱估测出该炔银簇化合物的带隙值为2.59eV，结果表明该炔银簇合物是潜在的半导体材料。在典型的三电极系统中测试了该炔银簇化合物的循环光电流响应曲线：将负载了该炔银簇合物的FTO导电玻璃作为工作电极，铂片电极作为辅助电极，银/氯化银作为参比电极，0.2MNa2SO4水溶液作为电解质。通过辐照开关循环测量0.6V电压下的光电流响应曲线(it曲线)。如图8所示，光电流的上升和下降与照射开关有很好的对应关系，当光照射时，光电流密度明显增加，当停止光照射时，光电流密度明显降低，这表明该炔银簇化合物在FTO电极中具有一定的光致电子/空穴对的产生和分离效率，几个开/关周期后，光电流密度都没有发生明显变化，表明该种炔银簇化合物的存在光化学稳定性，我们认为这类银簇材料在光电化学方面都具有潜在的应用前景。
如图9所示，研究了该炔银簇材料在室温下的固态光致发光。当激发光照射化合物时，原子基态被激发到激发态。该炔银簇材料在285nm激发时的最大发射波段为402nm。由于Ag离子的5s轨道是空的，所以电荷很容易从配位S原子的p轨道(填充轨道)转移到Ag离子的5s轨道上。也就是说，该炔银簇材料在402nm处的发射带可能是由于配体-金属电荷(LMCT)跃迁造成的，也可能是受到嗜银相互作用的干扰。此外，还对该炔银簇化合物进行了在不同溶剂中的荧光发射行为的实验探究。实验结果如图10、11所示，在甲醇、N，N-二甲基甲酰胺、乙腈、丙酮、三氯甲烷、乙醇和二氯甲烷这几种不同极性的溶剂中，相同的激发波长下，该炔银簇化合物的发射峰位置相差很小，在甲醇溶剂中该炔银簇化合物的发射峰强度最强，在二氯甲烷溶剂中，发射峰强度最弱，也几乎发生猝灭，同样可以说明溶剂的极性对该化合物的荧光发射峰强度有很大影响。该研究表明该炔银簇材料在荧光传感器方面有潜在的应用。
实施例1：
一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，包括以下步骤：
①称取[tBuC≡CAg]n(0.0945g，0.500mmol)，CF3COOAg(0.0440g，0.200mmol)以及H4TC4A(0.0288g，0.0400mmol)溶解在由6mL甲醇、6mL三氯甲烷以及2mL甲苯组成的溶剂中，混合均匀后得到浅黄色悬浊液；
②再迅速向该浅黄色悬浊液中加入1mL新制的1mg/mL NaBH4乙醇溶液后，溶液变成了棕黑色，在常温搅拌10分钟；将上述悬浊液在超声波振荡下搅拌30分钟后；
③转移至25mL聚四氟乙烯内衬的不锈钢高压反应釜中，再将密封好的不锈钢高压反应釜放入电热鼓风干燥箱内升温至65℃后恒温24小时，反应结束后待反应釜中悬浮液自然冷却至室温，得到淡黄色混合溶液，pH值为6.2；
④将淡黄色混合溶液过滤，得到淡黄色透明滤液；
⑤将所述淡黄色透明滤液在室温下挥发，2天后得到淡黄色的块状晶体，即为本发明一种硫杂杯[4]芳烃保护的炔银簇材料。
对于杯芳烃配体和炔银配体共同保护的银簇材料而言，其关键在于反应原料的配比，发明人在研发过程中，经过大量的实验发现：仅有按照本发明所述配比，才可以合成具有图1所示晶体结构的一种硫杂杯[4]芳烃保护的炔银簇材料。
实施例1所述的一种硫杂杯[4]芳烃保护的炔银簇材料具有良好的光电流响应特性：
在典型的三电极系统中测试了该炔银簇化合物的循环光电流响应曲线：取实施例1制得的具有良好的光电流响应特性和荧光传感性质的炔银簇材料样品负载到FTO导电玻璃作为工作电极，铂片电极作为辅助电极，银/氯化银作为参比电极，0.2M Na2SO4水溶液作为电解质。通过辐照开关循环测量0.6V电压下的光电流响应曲线(it曲线)。如图7所示，光电流的上升和下降与照射开关有很好的对应关系，当光照射时，光电流密度明显增加，当停止光照射时，光电流密度明显降低，这表明该炔银簇化合物在FTO电极中具有一定的光致电子/空穴对的产生和分离效率，几个开/关周期后，光电流密度(0.012μA/cm2)都没有发生明显变化，表明该种炔银簇化合物的存在光化学稳定性。上述所述的炔银簇材料具有良好的光电流响应特性，并具有化学稳定性，可应用于光电化学领域。
实施例1所述一种硫杂杯[4]芳烃保护的炔银簇材料的物理性能检测：
取实施例1制得的具有良好的光电流响应特性和荧光传感性质的炔银簇材料做进一步表征，其过程如下：
(1)晶体结构测定
配合物的X射线单晶衍射数据用大小合适的单晶样品在Bruker D8 QUEST型衍射仪收集测定。用石墨单色器，Mo-Kα(λ＝0.071073nm)为光源，数据还原用Saint软件包。用SHELXL-2014程序对结构进行解析，采用全矩阵最小二乘法(fill-matrix least-squaresrefinement based on F2)进行结构精修。
详细的晶体测定数据见表1，选择的键长数据见表2，Ag···Ag连接的距离见表3，选择的键角数据见表4，晶体结构图见图1，X-射线光电子能谱见图2，由图2可知该炔银簇中的Ag原子全部是+1价。粉末X-射线多晶衍射见图3，由图3可知，实验曲线和模拟曲线相一致，说明该炔银簇材料具有较高的纯度。红外光谱见图4。
表1：一种硫杂杯[4]芳烃保护的炔银簇材料的主要晶体学数据
aR1＝Σ||Fo|–|Fc||/Σ|Fo|；bwR2＝{Σ[w(Fo 2–Fc 2)2]/Σ[w(Fo 2)2]}1/2
表2：选择的键长
表3：Ag···Ag连接的距离
表4：选择的键角(°)
备注：对称代码:#1x,-y+1,z,#2-x+1,y,-z+1。
以上所述实施例，只是本发明的较佳实例，并非来限制本发明的实施范围，故凡依本发明申请专利范围所述的构造、特征及原理所做的等效变化或修饰，均应包括于本发明专利申请范围内。
Claims (7)
1.一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，其特征在于：所述炔银簇材料的化学式为：C133H165Ag18Cl3F6O14S8；
所述炔银簇材料属于单斜晶系，空间群为C2/m，晶胞参数为 α＝90°，β＝119.703(3)°，γ＝90°，/>
所述炔银簇材料的制备方法，包括以下步骤：
①将叔丁基炔银配体、CF3COOAg以及对叔丁基硫杂杯[4]芳烃溶解在溶剂中，混合均匀后得到悬浊液；
②迅速加入新制的NaBH4乙醇溶液后，常温搅拌10分钟，然后在超声波振荡下搅拌30分钟；
③然后转移至25mL聚四氟乙烯内衬的不锈钢高压反应釜中，将高压反应釜放入电热鼓风干燥箱内升温至65℃后恒温24小时，反应结束后冷却至室温，得到混合溶液；
④将混合溶液过滤得到滤液；
⑤将滤液挥发，得到块状晶体。
2.根据权利要求1所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，其特征在于：所述叔丁基炔银配体、CF3COOAg、对叔丁基硫杂杯[4]芳烃的摩尔比为12.5:5:1。
3.根据权利要求1所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，其特征在于：步骤①中所述溶剂是由甲醇、三氯甲烷以及甲苯组成的混合溶剂，所述甲醇、三氯甲烷、甲苯的体积比为3:3:1。
4.根据权利要求1所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，其特征在于：所述步骤③制备的混合溶液的pH值为6.0-6.5。
5.根据权利要求3所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法，其特征在于：所述步骤②中NaBH4乙醇溶液的浓度为1mg/mL，所述NaBH4乙醇溶液的体积是所述甲苯体积的一半。
6.根据权利要求1所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法制备所得到的材料作为催化剂在光电催化领域的应用。
7.根据权利要求1所述的一种硫杂杯[4]芳烃保护的炔银簇材料的制备方法制备所得到的材料在荧光传感器上的应用。
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