Ma Mingwei, Chen Enpeng, Yue Huijuan, Tian Ge, Feng Shouhua
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 130012, Changchun, P. R. China.
Nat Commun. 2025 Jan 3;16(1):367. doi: 10.1038/s41467-024-52225-5.
High-entropy metal-organic frameworks (HE-MOFs) hold promise as versatile materials, yet current rare examples are confined to low-valence elements in the fourth period, constraining their design and optimization for diverse applications. Here, a novel high-entropy, defect-rich and small-sized (32 nm) UiO-66 (ZrHfCeSnTi HE-UiO-66) has been synthesized for the first time, leveraging increased configurational entropy to achieve high tolerance to doping with diverse metal ions. The lattice distortion of HE-UiO-66 induces high exposure of metal nodes to create coordination unsaturated metal sites with a concentration of 322.4 μmol/g, which increases the abundance of Lewis acid-base sites, thereby achieving a significant improvement in the performance of the catalytic transfer hydrogenation (CTH) reaction. Systematic investigation manifests that the special electronic structure of HE-UiO-66 enhances the interaction and bonding with substrate molecules and reduces the energy barrier of the hydrogen transfer process. Our approach offers a new strategy for constructing coordination unsaturated metal sites in MOFs.
高熵金属有机框架材料（HE-MOFs）有望成为多功能材料，但目前为数不多的实例仅限于第四周期的低价元素，这限制了它们在各种应用中的设计与优化。在此，首次合成了一种新型的高熵、富含缺陷且尺寸小（32纳米）的UiO-66（ZrHfCeSnTi HE-UiO-66），利用增加的组态熵实现了对多种金属离子掺杂的高耐受性。HE-UiO-66的晶格畸变促使金属节点高度暴露，从而产生浓度为322.4 μmol/g的配位不饱和金属位点，这增加了路易斯酸碱位点的丰度，进而显著提高了催化转移氢化（CTH）反应的性能。系统研究表明，HE-UiO-66特殊的电子结构增强了与底物分子的相互作用和键合，并降低了氢转移过程的能垒。我们的方法为在金属有机框架材料中构建配位不饱和金属位点提供了一种新策略。
