Nanocluster superstructures assembled via surface ligand switching at high temperature
Grayson Johnson, Moon Young Yang, Chang Liu, Hua Zhou, Xiaobing Zuo, Diane A. Dickie, Sihan Wang, Wenpei Gao, Bukuru Anaclet, Frédéric A. Perras, Fuyan Ma, Chenjie Zeng, Da Wang, Sara Bals, Sheng Dai, Zhen Xu, Guoliang Liu, William A. Goddard III, Sen Zhang
Abstract
Superstructures with nanoscale building blocks, when coupled with precise control of the constituent units, open opportunities in rationally designing and manufacturing desired functional materials. Yet, synthetic strategies for the large-scale production of superstructures are scarce. We report a scalable and generalized approach to synthesizing superstructures assembled from atomically precise Ce₂₄O₂₈(OH)₈ and other rare-earth metal-oxide nanoclusters alongside a detailed description of the self-assembly mechanism. Combining operando small-angle X-ray scattering, ex situ molecular and structural characterizations, and molecular dynamics simulations indicates that a high-temperature ligand-switching mechanism, from oleate to benzoate, governs the formation of the nanocluster assembly. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, and furthermore, enables the synthesis of multicomponent superstructures. This synthetic approach, and the accurate mechanistic understanding, are promising for the preparation of superstructures for use in electronics, plasmonics, magnetics and catalysis.
Group Members
Johnson, G., Yang, M. Y., Liu, C., Zhou, H., Zuo, X., Dickie, D. A., Wang, S., Gao, W., Anaclet, B., Perras, F. A., Ma, F., Zeng, C., Wang, D., Bals, S., Dai, S., Xu, Z., Liu, G., III, W. A. G., & Zhang, S. (2023). Nanocluster superstructures assembled via surface ligand switching at high temperature. *Nature Synthesis*, *2*(9), 828-837. https://doi.org/10.1038/s44160-023-00304-8