Romero-Muñiz Ignacio, Romero-Muñiz Carlos, Del Castillo-Velilla Isabel, Marini Carlo, Calero Sofía, Zamora Félix, Platero-Prats Ana E
Departamento de Química Inorgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049 Madrid, Spain.
Departamento de Física Aplicada I, Universidad de Sevilla, E-41012 Seville, Spain.
ACS Appl Mater Interfaces. 2022 May 31;14(23):27040-7. doi: 10.1021/acsami.2c04712.
The metal-organic framework MOF-808 contains ZrO nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the ZrO nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol-benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditions.
金属有机框架MOF-808包含具有高密度空位的ZrO节点，这些空位可结合含羧酸盐的官能团来调节化学反应性。尽管用于修饰金属有机框架中ZrO节点化学性质的后合成方法是众所周知的，但从结构角度应对这些变化仍然是一个挑战。我们结合了红外光谱实验和第一性原理计算，以确定MOF-808内可用于化学修饰的节点空位的存在。我们展示了我们的方法评估用不同儿茶酚 - 苯甲酸酯配体修饰MOF-808节点的潜力。此外，我们应用了先进的同步加速器表征工具，如对分布函数分析和X射线吸收光谱，来解析后合成掺入儿茶酚基团中的单个金属位点的原子结构。最后，我们展示了这些用单个铜位点修饰的MOF-808材料对1,3 - 偶极环加成反应的催化活性。
