Yun Yapei, Fang Yaping, Fu Wengang, Du Wenjun, Zhu Yanan, Sheng Hongting, Astruc Didier, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui, 230601, China.
Université de Bordeaux, Talence Cedex, 33405, France.
Small. 2022 Apr;18(17):e2107459. doi: 10.1002/smll.202107459. Epub 2022 Mar 20.
Atom-precise nanoclusters-metal-organic framework (APNC/MOF) composites, as bifunctional material with well-defined structures, have attracted considerable attention in recent years. Despite the progress made to date, there is an urgent need to develop a generic and scalable approach for all APNCs. Herein, the authors present the Exploiting Fracture Strategy (EFS) and successfully construct a super-stable bifunctional APNC/ZIF-8(300 °C) composite overcoming the limitations of previous strategies in selecting APNCs. The EFS utilizes the fracture of ZnN in ZIF-8 after annealing at 300 °C. This method is suitable for all kinds of S/P protected APNCs with different sizes, including uncharged clusters Au Ag , Ag , negatively charged Au Ag , positively charged Ag Au , Au Cu and P-ligand-protected Pd Cl. Importantly, the generated APNC/MOF show significantly improved performances, for example, the activities of Au Ag /ZIF-8(300°C), Au Cu /ZIF-8(300°C), and Au Ag /ZIF-8(300°C) in the corresponding reactions are higher than those of Au Ag , Au Cu , and Au Ag , respectively. In particular, Au Ag /ZIF-8(300 °C) shows higher activity than Au Ag @ZIF-8. Therefore, this work offers guidance for the design of bifunctional APNC/MOF composites with excellent optimization of properties and opens up new horizons for future related nanomaterial studies and nanocatalyst designs.
原子精确的纳米团簇-金属有机框架（APNC/MOF）复合材料作为具有明确结构的双功能材料，近年来受到了广泛关注。尽管迄今为止已取得了进展，但迫切需要为所有APNC开发一种通用且可扩展的方法。在此，作者提出了利用断裂策略（EFS），并成功构建了一种超稳定的双功能APNC/ZIF-8（300°C）复合材料，克服了先前策略在选择APNC方面的局限性。EFS利用ZIF-8在300°C退火后ZnN的断裂。该方法适用于各种不同尺寸的S/P保护的APNC，包括不带电荷的团簇Au Ag 、Ag 、带负电荷的Au Ag 、带正电荷的Ag Au 、Au Cu 以及P-配体保护的Pd Cl。重要的是，生成的APNC/MOF表现出显著改善的性能，例如，Au Ag /ZIF-8（300°C）、Au Cu /ZIF-8（300°C）和Au Ag /ZIF-8（300°C）在相应反应中的活性分别高于Au Ag 、Au Cu 和Au Ag 。特别是，Au Ag /ZIF-8（300°C）表现出比Au Ag @ZIF-8更高的活性。因此，这项工作为设计具有优异性能优化的双功能APNC/MOF复合材料提供了指导，并为未来相关纳米材料研究和纳米催化剂设计开辟了新的视野。
