Han Bingyan, Hu Xixi, Yu Mingbo, Peng Tingting, Li Ying, He Gaohong
State Key Laboratory of Fine Chemicals, School of Petroleum and Chemical Engineering, Dalian University of Technology Panjin Liaoning 124221 China
RSC Adv. 2018 Jun 20;8(40):22748-22754. doi: 10.1039/c8ra03632b. eCollection 2018 Jun 19.
The encapsulation of Cu nanoclusters (Cu NCs) in metal-organic frameworks (MOFs) would improve the properties of Cu NCs. So far, these composites were reported by a two-step synthesis process. In this work, a facile one-pot synthesis of hybridization of glutathione (GSH) protected Cu NCs (Cu NCs@GSH) and MOF-5 (Cu NCs@GSH/MOFs) composites was reported for the first time. The results of UV-vis, TEM, XPS and SEM proved Cu NCs@GSH were distributed homogeneously over the entire MOF structure. The fluorescence intensity of Cu NCs encapsulated in MOF-5 was enhanced about 35-fold owing to the confining scaffold of the MOF and the stability was extended from 3 days to 3 months. Cu NCs@GSH/MOFs composites exhibited strong orange fluorescence and the emissions could change between blue, orange and red as they were partially reversible in different pH environments. This one-pot synthetic strategy could be extended for the encapsulation of fluorescent Ag NCs in MOFs as well. As-prepared Cu NCs@GSH/MOF-5 composites had high stability, and were easily recycled by centrifugation in aqueous solution, therefore, it would be utilized to develop a reusable sensor for detection of metal ions in the future.
将铜纳米团簇(Cu NCs)封装在金属有机框架(MOFs)中可改善Cu NCs的性能。到目前为止,这些复合材料是通过两步合成法报道的。在这项工作中,首次报道了一种简便的一锅法合成谷胱甘肽(GSH)保护的Cu NCs(Cu NCs@GSH)与MOF-5的杂化材料(Cu NCs@GSH/MOFs)。紫外可见光谱、透射电子显微镜、X射线光电子能谱和扫描电子显微镜的结果证明,Cu NCs@GSH均匀分布在整个MOF结构上。由于MOF的限制支架作用,封装在MOF-5中的Cu NCs的荧光强度增强了约35倍,并且稳定性从3天延长到了3个月。Cu NCs@GSH/MOFs复合材料呈现出强烈的橙色荧光,并且在不同pH环境下,由于其部分可逆性,其发射光可在蓝色、橙色和红色之间变化。这种一锅法合成策略也可扩展用于在MOFs中封装荧光银纳米团簇。所制备的Cu NCs@GSH/MOF-5复合材料具有高稳定性,并且在水溶液中通过离心很容易回收,因此,未来可用于开发一种可重复使用的金属离子检测传感器。