碳龙配合物修饰的石墨双炔的合成及其电催化氮气还原研究

近年来，石墨炔作为一种新型的二维碳材料，因其独特的结构特征引起了越来越多的关注。石墨炔仅由sp 和sp2 杂化的碳原子组成，可以看作用炔键将苯环相互连接起来而形成的一种二维材料。石墨炔中炔键与苯环形成的大共轭体系使其具有较高的电导率以及结构稳定性，本征的空洞结构提供了良好的传质条件，使其逐渐成为一种优质的催化剂基底材料。已有很多报道使用石墨炔负载各种金属单原子、团簇和纳米粒子的工作，并且于各种催化反应中均有应用，然而对于石墨炔负载分子却罕有人研究。我们基于溶液法合成石墨炔的炔炔键偶联机理，向合成石墨炔前体中加入含有端基炔结构的分子，将分子通过共价连接形式负载到了石墨炔中，成功实现基底材料和分子负载的一步反应。
本课题研究内容如下：
（1） 以三乙炔基苯为前体，在吡啶溶液中于铜片表面以Glaser-Hey 偶联制备石墨炔衍生物-氢取代石墨炔（Hydrogen substituted Graphdiyne，HsGDY），并以此为模板反应，在反应前体三乙炔基苯中加入含有端基炔的碳龙配合物，实现将碳龙配合物以共价连接的方式负载到HsGDY 基底上，并通过Talos 透射电子显微镜、双球差校正透射电子显微镜、拉曼光谱、红外光谱、X 射线衍射、X 射线光电子能谱等对其表征并证明了碳龙配合物的成功负载，实现了共价连接的均相分子非均相化。
（2） 对合成出的氢取代石墨炔负载的碳龙配合物Os@HsGDY 进行电催化氮气还原性能测试。搭建了一套精密且严谨的电催化氮气还原装置，包括严格的氮气纯化装置和用于电解的H 型电解池，使用阳离子色谱检测电解液中的铵根离子浓度进而计算得到法拉第效率和氨产率来确定Os@HsGDY 的电催化氮气还原性能。结果表明相较于原本无电催化氮气还原性能的碳龙分子，负载后的Os@HsGDY 具有一定的氮还原催化性能。虽然相较于目前已经报道的一些氮还原催化剂，Os@HsGDY 在性能上仍有一定差距，然而其具有优异的稳定性和可回收性，这也为众多高性能却难以持续稳定和回收利用的均相分子催化剂的非均相化提供了一个可行的方案。

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