Liu Zhendong, Zhao Wenyang, Kumar Prashant, Li Xinyu, Al Wahedi Yasser, Mkhoyan K Andre, Tsapatsis Michael, Stein Andreas
Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN, 55455, USA.
Department of Chemistry, University of Minnesota, Minneapolis, MN, 55455, USA.
Angew Chem Int Ed Engl. 2018 Nov 26;57(48):15707-15711. doi: 10.1002/anie.201808826. Epub 2018 Nov 2.
While bottom-up syntheses of ordered nanostructured materials at colloidal length scales have been successful at producing close-packed materials, it is more challenging to synthesize non-close-packed (ncp) structures. Here, a metal oxide nanostructure with ncp hollow sphere arrays was synthesized by combining a polymeric colloidal crystal template (CCT) with a Pechini precursor. The CCT provided defined confinement through its tetrahedral (T ) and octahedral (O ) voids where the three-dimensionally (3D) ordered, ncp hollow sphere arrays formed as a result of a crystallization-induced rearrangement. This nanostructure, consisting of alternating, interconnected large and small hollow spheres, is distinct from the inverse opal structures typically generated from these CCTs. The morphology of the ncp hollow sphere arrays was retained in pseudomorphic transformations involving sulfidation and reoxidation cycling despite the segregation of zinc during these steps.
虽然在胶体长度尺度上对有序纳米结构材料进行自下而上的合成已成功制备出密堆积材料，但合成非密堆积（ncp）结构更具挑战性。在此，通过将聚合物胶体晶体模板（CCT）与佩琴尼前驱体相结合，合成了具有ncp空心球阵列的金属氧化物纳米结构。CCT通过其四面体（T）和八面体（O）空隙提供了确定的限制，在这些空隙中，由于结晶诱导的重排形成了三维（3D）有序的ncp空心球阵列。这种由交替、相互连接的大空心球和小空心球组成的纳米结构，不同于通常由这些CCT产生的反蛋白石结构。尽管在这些步骤中锌会发生偏析，但ncp空心球阵列的形态在涉及硫化和再氧化循环的赝同形转变中得以保留。
