Zhang Dayu School of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China.
Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, 281, Krijgslaan (S3), Ghent B-9000, Belgium.
J Am Chem Soc. 2021 Dec 29;143(51):21511-21518. doi: 10.1021/jacs.1c05357. Epub 2021 Dec 7.
The differentiation between missing linker defects and missing cluster defects in MOFs is difficult, thereby limiting the ability to correlate materials properties to a specific type of defects. Herein, we present a novel and easy synthesis strategy for the creation of solely "missing cluster defects" by preparing mixed-metal (Zn, Zr)-UiO-66 followed by a gentle acid wash to remove the Zn nodes. The resulting material has the UiO-66 structure, typical for well-defined missing cluster defects. The missing clusters are thoroughly characterized, including low-pressure Ar-sorption, iDPC-STEM at a low dose (1.5 pA), and XANES/EXAFS analysis. We show that the missing cluster UiO-66 has a negligible number of missing linkers. We show the performance of the missing cluster UiO-66 in CO sorption and heterogeneous catalysis.
MOFs 中缺失连接体缺陷和缺失团簇缺陷的区分较为困难，从而限制了将材料性能与特定类型的缺陷相关联的能力。在此，我们提出了一种新颖且简便的合成策略，通过制备混合金属（Zn、Zr）-UiO-66 随后进行温和的酸洗以去除 Zn 节点，从而可以仅生成“缺失团簇缺陷”。所得材料具有 UiO-66 结构，典型的具有明确缺失团簇缺陷。对缺失团簇进行了彻底的表征，包括低压 Ar 吸附、低剂量（1.5 pA）的 iDPC-STEM 以及 XANES/EXAFS 分析。我们表明，缺失团簇 UiO-66 的缺失连接体数量可以忽略不计。我们展示了缺失团簇 UiO-66 在 CO 吸附和多相催化中的性能。
