CN112387294A - 一种负载钯的十钼酸铵催化剂材料的制备方法 - Google Patents
一种负载钯的十钼酸铵催化剂材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种负载钯的十钼酸铵催化剂材料的制备方法。本发明以七钼酸铵和醋酸钯为原料，通过溶剂热的方法一步合成负载钯的十钼酸铵材料，该材料具有良好的催化性能，能够高效催化碳碳偶联反应的合成，催化剂能够多次循环使用，催化反应的溶剂为水和乙醇，污染小，该催化剂在生物医药合成和催化材料领域具有广阔的应用前景。本发明反应条件温和、成本低廉，设备投资少，适合批量生产。
Description
技术领域
本发明属于化学领域，具体涉及一种负载钯的十钼酸铵催化剂材料的制备方法。
背景技术
溶剂热法起源于19世纪中叶，起初是用来模拟自然界成矿作用。1900年后水热法开始转向材料方面的研究。溶剂热法属于液相化学的范畴，是指在密闭的压力容器中，以水、乙醇等为溶剂，在高温高压的条件下，将不溶或者难溶的物质在水热条件下进行，通过控制高压釜内溶液的温差使产生对流以形成过饱和状态而析出生长晶体的方法。溶剂热法反应类型有很多种，包括热氧化、热还原、热沉淀、热合成、热水解、热结晶等。水热法工艺简单，反应条件容易控制，由于不需要对物质进行高温灼烧和研磨，不会造成结构的缺陷，所以得到的产物具有很好的结晶性。
钼酸铵分为二钼酸铵，四钼酸铵，七钼酸铵，十钼酸铵和十二钼酸铵。主要用途有以下几部分，一是工业上冶炼钼铁，制取金属钼粉用于钨钼合金、钼丝的原料；二是化工上合成三氧化钼和二氧化钼主要原材料；三是医药方面，为多种酶的组成部分，钼的缺乏会导致龋齿、肾结石、克山病、大骨节病、食道癌等疾病，另外钼酸铵具有一定的催化氧化活性。十钼酸铵是一种常用的钼酸铵。目前，十钼酸铵被广泛地用于染料、颜料、催化剂、防火剂、微量元素肥料、陶瓷色料及合成其它化合物的原料。但是，现在工业上合成十钼酸铵普遍的方法都需要在水溶液中进行反应，大致合成路径包括酸沉、氨溶、蒸发结晶等一系列工序得到目标产品。钼酸铵负载微量的钯能够大大提高其催化活性，另一方面可以减少贵金属钯的用量，节省成本。
发明内容
本发明所要解决的技术问题是针对现有技术，提供一种负载钯的十钼酸铵催化剂材料的制备方法。
本发明为解决上述技术问题所采取的技术方案为：一种负载钯的十钼酸铵催化剂材料的制备方法是通过水热法一步合成的，具体包括以下步骤。
1）称取一定量的七钼酸铵置于烧瓶中，添加少量的醋酸钯，一定体积的蒸馏水和乙醇，超声30分钟，然后再搅拌20分钟，得到混合物悬浊液溶；
2）将上述混合物悬浊液溶转移到具有50 mL的不锈钢反应釜中，将反应釜放入鼓风干燥箱中，150 ~ 180℃恒温反应24 ~ 72 h；
3）反应结束后，自然冷却至室温，收集沉淀，用甲醇洗涤，然后干燥，得到浅黄色的固体粉末，即为一种负载钯的十钼酸铵催化剂材料；
所述七钼酸铵化学式为(NH4)6Mo7O24；
所述十钼酸铵化学式为(NH4)8Mo10O34。
进一步的，本发明还提供了所述的一种负载钯的十钼酸铵催化剂材料的用途，该材料作为Suzuki偶联反应的催化剂，以4-溴吡啶和4-吡啶硼酸为原料，在乙醇和DMF体积比为1:1的混合溶剂中，温度为50℃，反应24 h后，4,4’-二联吡啶产品的产率达85 %，催化剂循环使用3次以后，在反应条件相同的情况下，产品产率达79%以上。
与现有技术相比，本发明获得材料的特点如下：
将七钼酸铵、醋酸钯、蒸馏水和乙醇通过溶剂热的方法一步合成负载钯的十钼酸铵材料，该材料具有良好的催化性能，能够高效催化碳碳偶联反应的合成；本实验过程不涉及副反应的发生，不涉及污染性的溶剂；残余溶剂中的乙醇能够通过蒸馏回收利用，极大的节省了资源的消耗，且不会造成浪费和污染。
附图说明
图1是实施例1所制得的催化剂材料的粉末衍射图；
图2是实施例1所制得的催化剂材料的SEM图。
具体实施方式
以下结合实施例对本发明作进一步详细描述，本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。
实施例1
称取10 g的七钼酸铵置于烧瓶中，添加0.1 g的醋酸钯，10 mL蒸馏水和30 mL乙醇，超声30分钟，然后再搅拌20分钟，得到混合物悬浊液溶；将上述混合物悬浊液溶转移到50 mL的不锈钢反应釜中，将反应釜放入鼓风干燥箱中，150 ℃恒温反应72 h；反应结束后，自然冷却至室温，收集沉淀，用甲醇洗涤，然后干燥，得到浅黄色的固体粉末，即为一种负载钯的十钼酸铵催化剂材料。用粉末衍射(XRD)仪测试材料的组成结构（图1）；用扫描电镜(SEM)观察所述材料的形貌为块状（图2）。
称取实施例1中所制备的负载钯的十钼酸铵催化剂材料0.1克作为催化剂添加到圆底烧瓶中，添加1.0 mmol的4-溴吡啶和1.0 mmol的4-吡啶硼酸，添加10 mL无水乙醇和10mL的DMF，除去烧瓶中的氧气，在氮气氛围下，50 ℃反应24 h，反应结束自然冷却到室温，除去溶剂，得到浅黄色粗产品，柱色谱分离，得到纯的0.85 mmol的4,4’-二联吡啶产品，催化剂循环使用3次以后，在反应条件相同的情况下，产品产率达79%以上。
实施例2
称取20 g的七钼酸铵置于烧瓶中，添加0.2 g的醋酸钯，20 mL蒸馏水和30 mL乙醇，超声30分钟，然后再搅拌20分钟，得到混合物悬浊液溶；将上述混合物悬浊液溶转移到80 mL的不锈钢反应釜中，将反应釜放入鼓风干燥箱中，180 ℃恒温反应24 h；反应结束后，自然冷却至室温，收集沉淀，用甲醇洗涤，然后干燥，得到浅黄色的固体粉末，即为一种负载钯的十钼酸铵催化剂材料。用粉末衍射仪测试材料的组成结构；用扫描电镜(SEM)观察所述材料的形貌。以所制备的材料作为Suzuki偶联反应的催化剂，以4-溴吡啶和4-吡啶硼酸为反应原料，在乙醇和DMF体积比为1:1的混合溶剂中，反应温度为50 ℃，进行合成4,4’-二联吡啶产品的实验，产率达85.5 %，催化剂循环使用3次以后，在反应条件相同的情况下，产品产率达80%以上。
实施例3
称取10 g的七钼酸铵置于烧瓶中，添加0.1 g的醋酸钯，10 mL蒸馏水和30 mL乙醇，超声30分钟，然后再搅拌20分钟，得到混合物悬浊液溶；将上述混合物悬浊液溶转移到50 mL的不锈钢反应釜中，将反应釜放入鼓风干燥箱中，160 ℃恒温反应60 h；反应结束后，自然冷却至室温，收集沉淀，用甲醇洗涤，然后干燥，得到浅黄色的固体粉末，即为一种负载钯的十钼酸铵催化剂材料。用粉末衍射(XRD)仪测试材料的组成结构；用扫描电镜(SEM)观察所述材料的形貌。以所制备的材料作为Suzuki偶联反应的催化剂，以4-溴吡啶和4-吡啶硼酸为反应原料，在乙醇和DMF体积比为1:1的混合溶剂中，反应温度为50 ℃，进行合成4,4’-二联吡啶产品的实验，产率达86 %，催化剂循环使用3次以后，在反应条件相同的情况下，产品产率达80%以上。
Claims (2)
1.一种负载钯的十钼酸铵催化剂材料的制备方法，其特征在于，所述制备方法包括以下步骤：
1）称取一定量的七钼酸铵置于烧瓶中，添加少量的醋酸钯，一定体积的蒸馏水和乙醇，超声30分钟，然后再搅拌20分钟，得到混合物悬浊液溶；
2）将上述混合物悬浊液溶转移到具有50 mL的不锈钢反应釜中，将反应釜放入鼓风干燥箱中，150 ~ 180℃恒温反应24 ~ 72 h；
3）反应结束后，自然冷却至室温，收集沉淀，用甲醇洗涤，然后干燥，得到浅黄色的固体粉末，即为一种负载钯的十钼酸铵催化剂材料；
所述七钼酸铵化学式为(NH4)6Mo7O24；
所述十钼酸铵化学式为(NH4)8Mo10O34。
2.一种如权利要求1所述制备方法制得的负载钯的十钼酸铵催化剂材料的用途，其特征在于，该材料作为Suzuki偶联反应的催化剂，以4-溴吡啶和4-吡啶硼酸为反应原料，在乙醇和DMF体积比为1:1的混合溶剂中，反应温度为50 ℃，反应24 h后，4,4’-二联吡啶产品的产率达85 %，催化剂循环使用3次以后，在反应条件相同的情况下，产品产率达79%以上。
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