CN112500580B - 一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用 - Google Patents
一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域，一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用，其中制备方法：是以吡唑配体H2DPA与金属钴盐中的Co2+作为节点，通过溶剂热法制得用于活化氧气分子的钴基金属有机框架催化剂，其合成路线如下：H2DPA+Co2+→Co‑DPA，金属钴盐选自氯化钴或硝酸钴中的一种。本发明制备的钴基金属有机框架催化剂在光催化活化氧气分子反应中的光电流测试对比图，可以看出，氧气氛围下Co‑DPA具有明显增大的光电流响应，表明Co‑DPA中还原态的Co具备活化氧气分子的能力。
Description
技术领域
本发明涉及一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用，属于光催化材料技术领域。
背景技术
金属有机框架(Metal-organic frameworks,MOFs)是一类由金属离子和有机配体通过配位键组装而成的高度有序的具有孔道结构的材料，由于构成其结构组分的几何形状、尺寸以及官能团特性不同，迄今为止已经研究报道了超过20000多种不同的MOFs。其比表面积约在1000到10000m2/g不等，显著地超过了传统多孔材料如沸石、活性炭等。同时由于其具有永久孔隙率以及其以及组分多元可变等特点，使得其在储存染料(氢气、甲烷等)、捕获CO2、活化氧气分子、催化等方面具有广泛的应用。
近些年来，绿色可持续发展越来越引起重视，开发氧化反应的绿色化技术刻不容缓。传统的金属催化剂虽然具备优秀的催化效率，但是无法重复利用，会造成资源上的浪费与环境污染。近些年兴起的固体材料非均相催化剂，氧气分子只能与其表面暴露的活性位点作用。金属有机框架得益于其多孔特性，内部的活性位点也可以与氧气分子发生作用。同时，金属有机框架是一种非均相催化剂，反应结束后可以通过较为便捷的方法从反应体系分离出来，经过清洗后可进行下一次催化反应，避免了资源浪费与环境污染。
发明内容
为了克服现有技术中存在的不足，本发明目的是提供一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用，为了提高氧气的活化效率，开发了一种钴基MOFs，一方面可以利用MOFs的多孔特性吸附氧气，钴节点的引入也进一步提高了氧气的吸附效率。同时，拟通过大芳环型蒽基配体与氧化还原活性的Co作为金属中心，其还原态能够还原O2生成活性氧物种，各种价态的Co中间体能够进一步以芬顿反应机制与活性氧物种反应，实现对有机底物氧化反应的介导。在非均相催化剂的结构设计中，以具有良好电子导通性的含氮配位基团连接光敏配体与金属中心；由于配体芳香堆积与氮-金属簇具有不同的电荷导通性和光响应机制，因此在光激发条件下，有望实现配体聚集单元与金属簇聚集单元高效的电荷分离，耦合O2还原和有机底物氧化，实现利用O2为绿色氧化剂的光催化氧化反应，制备高附加值精细化工中间体；金属有机框架材料的非均相特性有利于催化剂的回收。
为了实现上述发明目的，解决已有技术中所存在的问题，本发明采取的技术方案是：一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法，是以吡唑基配体H2DPA与金属钴盐中的Co2+作为节点，通过溶剂热法制得钴基金属有机框架催化剂，其合成路线如下：
H2DPA+Co2+→Co-DPA；
所述金属钴盐选自氯化钴或硝酸钴中的一种；
所述吡唑基配体H2DPA，分子式为C20H14N4，具有如下(A)
分子结构式，
所述Co-DPA的制备方法，包括以下步骤：
步骤1、将高氯酸锂、二氧化硅、蒽及N-溴代琥珀酰亚胺，按l：6～10：6～10：13～20的摩尔比加入250mL三口瓶中，而后向瓶中加入80～120mL二氯甲烷溶剂，在室温下搅拌25～40min，再将所得的黄色混合物过滤，在分液漏斗中用去离子水对所得滤液清洗，最后用旋蒸仪旋蒸所得有机相滤液，得到黄色粉末9,10-二溴蒽；
步骤2、将步骤1制得的9,10-二溴蒽、碳酸铯、四(三苯基膦)钯与4-吡唑硼酸频哪醇酯，按1:5～8:0.1～0.2:3～5的摩尔比置于250mL三口烧瓶中，用N2置换瓶中气体氛围三次，再将已经过脱气处理的10～20mL DMF加入其中，在105～115℃的条件下反应50～80h，反应结束后，将反应混合物倒入1L的烧杯中，加入500～700mL水并持续搅拌15～25min，而后过滤得到淡黄色反应粗产物，再将淡黄色反应粗产物溶于四氢呋喃中，用柱层析分离，流动相采用体积比为1:1丙酮与正己烷的混合溶剂，得到黄色粉末，即吡唑基配体H2DPA；
步骤3、将步骤2制得的吡唑基配体H2DPA与CoCl2·6H2O或Co(NO3)2·6H2O按1:4～5质量比加入到7mL的玻璃小瓶中，再加入2～4mL DEF与5～25μL乙酸，充分混合后搅拌均匀，首先将其放入水热高压釜中，然后再置于带有控温功能的烘箱中，经过8～12h的升温，使温度升至110～120℃，反应72～90h，最后经过8～12h降温至25℃，得到紫色棒状晶体，过滤后用DEF冲洗干净，置于空气中干燥，得到目标材料钴基金属有机框架催化剂Co-DPA；
所述方法制备的钴基金属有机框架催化剂在光催化活化氧气分子反应中的应用。
本发明有益效果是：一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法及其应用，其中制备方法：是以吡唑配体H2DPA与金属钴盐中的Co2+作为节点，通过溶剂热法制得用于活化氧气分子的钴基金属有机框架催化剂，其合成路线如下：
H2DPA+Co2+→Co-DPA；
所述方法制备的活化氧气分子的钴基金属有机框架催化剂Co-DPA通过晶体工程学手段，构筑分离柱堆积型金属有机框架，其中，蒽基配体通过zigzag型π-π堆积形成具有光敏性的一维链；Co金属中心通过配体端位的吡唑基团，形成Co-N-N-Co的一维链；两种一维链条在金属有机框架中呈平行排列，蒽基配体与Co之间的吡唑链接基团与蒽基配体处于近似垂直的排布；以上结构特色，保证了配体一维链在暗态下是绝缘的，但是能够在光激发下转为导通，作为光致电子转移的通道，实现高效电荷分离；同时，光激发也能够启动从蒽基配体到Co中心的光致电荷迁移，原位生成还原态Co物种，作为O2活化、还原的活性中心。
附图说明
图1是实施例1制得的配体H2DPA的核磁共振波谱图。
图2是实施例1制得的配体H2DPA的紫外可见吸收光谱图。
图3是实施例1目标材料Co-DPA的晶体结构示意图。
图4是实施例1目标材料Co-DPA的固体紫外吸收光谱图。
图5是实施例1目标材料Co-DPA的光照前后NIS阻抗对比图。
图6是实施例6目标材料Co-DPA的分别在氩气与氧气氛围下的光电流测试对比图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
将蒽(1.78g，10mmol)，N-溴代琥珀酰亚胺(3.56g，20mmol)，高氯酸锂(0.16g，1.5mmol)，二氧化硅(0.6g，10mmol)加入到250mL三口瓶中，而后向瓶中加入100mL二氯甲烷溶剂。在室温下搅拌35min，再将所得的黄色混合物过滤，在分液漏斗中用去离子水对所得滤液清洗。最后用旋蒸仪旋蒸所得有机相滤液，得到黄色粉末9,10-二溴蒽3.2g；
称取9,10-二溴蒽(1.098g,3mmol)、碳酸铯(5.868g，18mmol)、四(三苯基膦)钯(0.5g，0.43mmol)与4-吡唑硼酸频哪醇酯(2.328g，12mmol)置于250mL三口烧瓶中，用N2置换瓶中气体氛围三次。再将已经过脱气处理的15mL DMF加入其中，在110℃的条件下反应60h。反应结束后，将反应混合物倒入1L的烧杯中，加入600mL水并持续搅拌15min，而后过滤得到淡黄色反应粗产物。再将淡黄色反应粗产物溶于四氢呋喃中，用柱层析分离，流动相采用体积比为1:1丙酮与正己烷的混合溶剂，得到黄色粉末，即吡唑基配体H2DPA 0.8g。核磁共振波谱图，如图1所示，紫外可见吸收光谱图，如图2所示。
称取10mg H2DPA与40mg CoCl2·6H2O加入到7mL的玻璃小瓶中，再加入3mL DEF与20μL乙酸。充分混合后搅拌均匀，首先将其放入水热高压釜中，然后再置于带有控温功能的烘箱中，先经过8h的升温，使温度升至110℃，反应90h，最后经过10h降温至25℃，得到紫色棒状晶体。过滤后用DEF冲洗干净，置于空气中干燥，得到目标材料钴基金属有机框架催化剂Co-DPA 10mg，产率75％，晶体结构示意图，如图3所示，固体紫外吸收光谱图，如图4所示，光照前后NIS阻抗对比图，如图5所示。
实施例2
称取10mg H2DPA与40mg CoCl2·6H2O加入到7mL的玻璃小瓶中，再加入3mLDEF与20μL乙酸。充分混合后搅拌均匀，首先将其放入水热高压釜中，然后再置于带有控温功能的烘箱中，先经过8h的升温，使温度升至110℃，反应90h，最后经过10h降温至25℃，得到紫色棒状晶体。过滤后用DEF冲洗干净，置于空气中干燥，得到目标材料钴基金属有机框架催化剂Co-DPA9 mg，产率68％。
实施例3
称取10mg H2DPA与45mg Co(NO3)2·6H2O加入到7mL的玻璃小瓶中，再加入3mLDEF与20μL乙酸。充分混合后搅拌均匀，首先将其放入水热高压釜中，然后再置于带有控温功能的烘箱中，先经过8h的升温，使温度升至110℃，反应90h，最后经过10h降温至25℃，得到紫色棒状晶体。过滤后用DEF冲洗干净，置于空气中干燥，得到目标材料钴基金属有机框架催化剂Co-DPA 8mg，产率60％。
实施例4
向光反应管中加入10mg Co-DPA与苄胺(32mg，0.3mmol)，并加入3mL乙腈溶剂。波长为405nm的LED为光源，在氧气氛围、30℃下反应12h。将反应液用乙酸乙酯进行萃取后并用水洗涤、干燥、浓缩，通过薄层层析分离产物，通过核磁表征产物N-苄烯丁胺，产率90％。该非均相催化氧化可对苄胺底物进行拓展，如表1所示。
表1
实施例5
向光反应管中加入10mg Co-DPA与2-苯基-1,2,3,4-四氢异喹啉(68.7mg，0.3mmol)，并加入3mL乙腈溶剂。在波长为405nm的LED光源照射下，在氧气氛围下保持30℃反应12h。将反应液用乙酸乙酯进行萃取后并用水洗涤、干燥、浓缩，通过薄层层析分离产物，通过核磁表征产物1(2H)-异喹啉酮，3,4-二氢-2-苯基，产率92％。该非均相催化氧化可对苄胺底物进行拓展，如表2所示。
表2
实施例6
分别取5mg的Co-DPA加入到5mL的乙醇中制成悬浮液，然后分别加入0.5mL的Nafin并通过超声混合，分别取80μL悬浮液涂敷于FTO玻璃表面，涂敷面积为1cm2，烘干，然后将FTO玻璃夹在电极夹上，作为工作电极。光电流测试在CHI 660E电化学工作站进行，采用三电极体系，Ag/AgCl电极作为参比电极，铂片作为对电极，3M的氯化钾水溶液作为电解液，光电流测试分别在氩气氛围下和1atm的氧气氛围下测试，温度为室温，光源为30W的405nm波长LED。光电流测试对比图，如图6所示，可以看出，氧气氛围下Co-DPA具有明显增大的光电流响应，表明Co-DPA中还原态的Co具备活化氧气的能力。
Claims (2)
1.一种用于活化氧气分子的钴基金属有机框架催化剂的制备方法，其特征在于：是以吡唑基配体H2DPA与金属钴盐中的Co2+作为节点，通过溶剂热法制得钴基金属有机框架催化剂，其合成路线如下：
H2DPA+Co2+→Co-DPA；
所述金属钴盐选自氯化钴或硝酸钴中的一种；
所述吡唑基配体H2DPA，分子式为C20H14N4，具有如下(A)
分子结构式，
所述Co-DPA的制备方法，包括以下步骤：
步骤1、将高氯酸锂、二氧化硅、蒽及N-溴代琥珀酰亚胺，按l：6～10：6～10：13～20的摩尔比加入250mL三口瓶中，而后向瓶中加入80～120mL二氯甲烷溶剂，在室温下搅拌25～40min，再将所得的黄色混合物过滤，在分液漏斗中用去离子水对所得滤液清洗，最后用旋蒸仪旋蒸所得有机相滤液，得到黄色粉末9,10-二溴蒽；
步骤2、将步骤1制得的9,10-二溴蒽、碳酸铯、四(三苯基膦)钯与4-吡唑硼酸频哪醇酯，按1:5～8:0.1～0.2:3～5的摩尔比置于250mL三口烧瓶中，用N2置换瓶中气体氛围三次，再将已经过脱气处理的10～20mL DMF加入其中，在105～115℃的条件下反应50～80h，反应结束后，将反应混合物倒入1L的烧杯中，加入500～700mL水并持续搅拌15～25min，而后过滤得到淡黄色反应粗产物，再将淡黄色反应粗产物溶于四氢呋喃中，用柱层析分离，流动相采用体积比为1:1丙酮与正己烷的混合溶剂，得到黄色粉末，即吡唑基配体H2DPA；
步骤3、将步骤2制得的吡唑基配体H2DPA与CoCl2·6H2O或Co(NO3)2·6H2O按1:4～5质量比加入到7mL的玻璃小瓶中，再加入2～4mL DEF与5～25μL乙酸，充分混合后搅拌均匀，首先将其放入水热高压釜中，然后再置于带有控温功能的烘箱中，经过8～12h的升温，使温度升至110～120℃，反应72～90h，最后经过8～12h降温至25℃，得到紫色棒状晶体，过滤后用DEF冲洗干净，置于空气中干燥，得到目标材料钴基金属有机框架催化剂Co-DPA。
2.根据权利要求1所述方法制备的钴基金属有机框架催化剂在光催化活化氧气分子反应中的应用。
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