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Modulator-directed assembly of hybrid composites based on metal-organic frameworks and upconversion nanoparticles

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Abstract

Hybrid composites made of metal-organic frameworks (MOFs) and lanthanide-doped upconversion nanoparticles (UCNPs) have attracted considerable interest for their synergistically enhanced functions in various applications such as chemical sensing, photocatalysis, anticounterfeiting and nanomedicine. However, precise assembly of MOF/UCNP hybrid composites with tunable morphologies remains a challenge due to the lack of effective synthetic methods and fundamental understanding of the growth mechanisms. Herein, we propose a modulator-directed assembly strategy to synthesize a series of ZIF-8@UCNP composites (ZIF-8 = zeolitic imidazolate framework-8). The UCNPs densely paved on the surface of ZIF-8 microcrystals and endowed the composites with intense upconversion blue emission, which were verified by steady-state/transient photoluminescence (PL) spectroscopy and single-particle imaging. Ethylenediamine (EDA) was firstly used as a modulator to fine-tune the predominant MOF facets and realized distinct morphologies of the composites. By adjusting the concentration of EDA from 0 to 25 mmol/L, the morphology of the ZIF-8@UCNP composites was tuned from rhombic dodecahedron (RD) to truncated rhombic dodecahedron (TRD), cube with truncated edges (CTE), cube, and finally a unique form of interpenetration twins (IT). The nucleation and growth process of the ZIF-8@UCNP composites was monitored by time-dependent scanning electron microscopy (SEM) images and the formation mechanism was thoroughly revealed. Furthermore, we demonstrated that the strategy for assembly of morphology-controllable ZIF-8@UCNP composites was generally applicable to various UCNPs with different sizes and shapes. The proposed strategy is expected to open up new avenues for the controllable synthesis of MOF/UCNP composites toward diverse applications.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC) (Nos. U1805252, 22175179, 22135008, 12174392, 21975257, and 12104456), NSF of Fujian Province (Nos. 2021I0040, 2021L3024), and the Chinese Academy of Sciences/State Administration of Foreign Experts Affairs (CAS/SAFEA) International Partnership Program for Creative Research Teams.

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  1. CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Yanhui Feng, Xingjun Li, Shan Lu, Renfu Li, Zhongliang Gong, Xiaoying Shang, Yifan Pei, Wei Zheng, Datao Tu & Xueyuan Chen

  2. College of chemistry, Fuzhou university, Fuzhou, 350108, China

    Yanhui Feng, Xingjun Li & Xueyuan Chen

  3. Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, 350108, China

    Xueyuan Chen

  4. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350117, China

    Yifan Pei & Xueyuan Chen

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  1. Yanhui Feng
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Feng, Y., Li, X., Lu, S. et al. Modulator-directed assembly of hybrid composites based on metal-organic frameworks and upconversion nanoparticles. Nano Res. 16, 1482–1490 (2023). https://doi.org/10.1007/s12274-022-4684-9

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