Huang Wengang, Xue Wen-Long, Chen Peng, Wang Zhiliang, Lin Rijia, Zhao Shuke, Yu Shuwen, Chen Yuelei, Zha Xiangyi, Appadoo Dominique, Tian Tian, Chen Vicki, Henke Sebastian, Cheetham Anthony K, Wang Lianzhou, Hou Jingwei
School of Chemical Engineering, The University of Queensland, Saint Lucia, QLD, 4072, Australia.
Anorganische Chemie, Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn Straße 6, 44227, Dortmund, Germany.
Angew Chem Int Ed Engl. 2025 Aug 4;64(32):e202506570. doi: 10.1002/anie.202506570. Epub 2025 Jun 12.
Modulating the liquid phase of metal-organic frameworks (MOFs) presents new opportunities for functionalizing glassy MOFs, expanding the fundamental science and practical application for this emerging family of materials. Herein, we report the fabrication of a bimetallic glassy MOF via a liquid-liquid transition process. This is achieved by introducing a robust Schiff base-cobalt functional group into Zn-ZIF-62, which attracts negatively charged imidazolate ligands, facilitating low-temperature melting. This ultimately leads to the formation of a bimetallic glassy MOF (Co/Zn-aZIF-62-ipy) upon melt-quenching. The material features an exceptionally high glass-forming capability, uniformly distributed bimetallic ions, and a markedly enhanced visible light photogeneration efficiency of enzymatically active nicotinamide adenine dinucleotide (NADH) when compared with Co-doped ZIF-62 glass. These findings offer novel insights into modulating the liquid phase of an MOF to develop functional glassy MOF photocatalysts for coenzyme NADH regeneration and other advanced applications.
调节金属有机框架(MOF)的液相为玻璃态MOF的功能化带来了新机遇,拓展了这一新兴材料家族的基础科学和实际应用。在此,我们报道了通过液 - 液转变过程制备双金属玻璃态MOF。这是通过将一个稳定的席夫碱 - 钴官能团引入Zn - ZIF - 62来实现的,该官能团吸引带负电荷的咪唑盐配体,促进低温熔化。这最终导致在熔体淬火后形成双金属玻璃态MOF(Co/Zn - aZIF - 62 - ipy)。与钴掺杂的ZIF - 62玻璃相比,该材料具有极高的玻璃形成能力、均匀分布的双金属离子以及显著提高的酶活性烟酰胺腺嘌呤二核苷酸(NADH)的可见光光生效率。这些发现为调节MOF液相以开发用于辅酶NADH再生及其他先进应用的功能性玻璃态MOF光催化剂提供了新见解。