Mu Wen-Lei, Li Lanyan, Cong Xu-Zi, Chen Xinyu, Xia Pengkun, Liu Qingyi, Wang Likai, Yan Jun, Liu Chao
College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, PR China.
School of Resources and Environment, Hunan University of Technology and Business, Changsha, Hunan 410205, PR China.
J Am Chem Soc. 2024 Oct 4. doi: 10.1021/jacs.4c07518.
The pursuit of precision in the engineering of metal nanoparticle assemblies has long fascinated scientists, but achieving atomic-level accuracy continues to pose a significant challenge. This research sheds light on the hierarchical assembly processes of two high-nuclearity Cu(I) nanoclusters (NCs). By employing a multiligand cooperative stabilization strategy, we have isolated a series of thiacalix[4]arene (TC4A)/alkynyl coprotected Cu(I) NCs (, where = , , , ). These NCs are intricately coassembled from the fundamental building units of {Cu(TC4A)} and alkynyl-stabilized CuL in various ratios. By capturing active anion templates such as O, Cl, or C that are generated in situ, we have further explored the secondary structural self-assembly of these clusters. serves as a secondary assembly module for constructing and , which exhibit the highest nuclearity reported to date among Cu(I) NCs encased in macrocyclic ligands. Notably, demonstrates an impressive Faradaic efficiency of 62.01% for hydrocarbons at -1.57 V vs RHE during CO electroreduction, with 34.03% for CH and 27.98% for CH. This performance establishes it as an exceptionally rare, large, atomically precise metal NC (nuclearity >30) capable of catalyzing the formation of highly electro-reduced hydrocarbon products. Our research has introduced a new approach for constructing high-nuclearity Cu(I) NCs through a hierarchical assembly method and investigating their potential in the electrocatalytic transformation of CO into hydrocarbons.
长期以来，科学家们一直着迷于在金属纳米颗粒组装工程中追求精确性，但实现原子级精度仍然是一项重大挑战。这项研究揭示了两种高核铜（I）纳米团簇（NCs）的分级组装过程。通过采用多配体协同稳定策略，我们分离出了一系列硫杂杯[4]芳烃（TC4A）/炔基共保护的铜（I）NCs（，其中 = ， ， ， ）。这些NCs由{Cu(TC4A)}和炔基稳定的CuL的基本构建单元以各种比例复杂地共组装而成。通过捕获原位生成的活性阴离子模板，如O、Cl或C，我们进一步探索了这些团簇的二级结构自组装。 用作构建 和 的二级组装模块，它们在大环配体包裹的铜（I）NCs中展现出迄今为止报道的最高核数。值得注意的是， 在-1.57 V（相对于可逆氢电极）的CO电还原过程中，对烃类的法拉第效率达到了令人印象深刻的62.01%，其中对CH的效率为34.03%，对CH的效率为27.98%。这种性能使其成为一种极其罕见的、大型的、原子精确的金属NC（核数>30），能够催化形成高度电还原的烃类产物。我们的研究引入了一种通过分级组装方法构建高核铜（I）NCs并研究其在将CO电催化转化为烃类中的潜力的新方法。
