Wang Nan, Li Xueping, Lian Xiaoyan, Zhuang Qian, Wang Jialu, Li Jin, Qian Huaming, Miao Kangkang, Wang Yan, Luo Xiaolin, Feng Guodong
Key Laboratory of Advanced Molecular Engineering Materials, Engineering Research Center for Titanium Based Functional Materials and Devices in Universities of Shaanxi Province, College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, P. R. China.
Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, College of Chemistry, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
Inorg Chem. 2024 Mar 4;63(9):4393-4403. doi: 10.1021/acs.inorgchem.4c00024. Epub 2024 Feb 20.
The immobilization of tiny active species within inert mesoporous silica imparts a range of functions, enhancing their applicability. A significant obstacle is the spontaneous migration and aggregation of these species within the mesopores, which threaten their uniform distribution. To address this, we propose a postmodification method that involves grafting transition metal oxide nanoclusters into silica mesopores via interfacial condensation, catalyzed by acetate ions. Specifically, CuO nanoclusters, in the form of oligomeric [O-Cu-(OH) ], have a strong interaction with the silica framework. This interaction inhibits their growth and prevents mesopore blockage. Theoretical calculation results reveal that the acetate ion promotes proton transfer among various hydroxy species, lowering the free energy and thereby facilitating the formation of Cu-O-Si bonds. This technique has also been successfully applied to the encapsulation of four other types of transition metal oxide nanoclusters. Our encapsulation strategy effectively addresses the challenge of dispersing transition metal oxides in mesoporous silica, offering a straightforward and widely applicable method for enhancing the functionality of mesoporous materials.
将微小的活性物种固定在惰性介孔二氧化硅中可赋予一系列功能，增强其适用性。一个重大障碍是这些物种在介孔内的自发迁移和聚集，这会威胁到它们的均匀分布。为了解决这个问题，我们提出了一种后修饰方法，该方法涉及通过乙酸根离子催化的界面缩合将过渡金属氧化物纳米团簇接枝到二氧化硅介孔中。具体而言，呈低聚物[O-Cu-(OH)]形式的CuO纳米团簇与二氧化硅骨架有很强的相互作用。这种相互作用抑制了它们的生长并防止介孔堵塞。理论计算结果表明，乙酸根离子促进了各种羟基物种之间的质子转移，降低了自由能，从而促进了Cu-O-Si键的形成。该技术也已成功应用于其他四种类型过渡金属氧化物纳米团簇的封装。我们的封装策略有效地解决了过渡金属氧化物在介孔二氧化硅中分散的挑战，为增强介孔材料的功能提供了一种简单且广泛适用的方法。
