Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis

• Published in: Angewandte Chemie 2020-03, Vol.132 (13), p.5364-5369
• Main Authors: Gong, Xuan, Shu, Yufei, Jiang, Zhuo, Lu, Lingxiang, Xu, Xiaohui, Wang, Chao, Deng, Hexiang
• Format: Article
• Language: English
• Subjects: Aktive Zentren; Catalysis; Catalysts; Catalytic activity; Chemistry; Crystallography; Dehydrierung; Dehydrogenation; Exploitation; Lattice vacancies; Metal-organic frameworks; Metall-organische Gerüste; Photocatalysis; Photokatalyse; Porphyrine; Room temperature; Vacancies
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201915537

Discoveries of the accurate spatial arrangement of active sites in biological systems and cooperation between them for high catalytic efficiency are two major events in biology. However, precise tuning of these aspects is largely missing in the design of artificial catalysts. Here, a series of metal–organic frameworks (MOFs) were used, not only to overcome the limit of distance between active sites in bio‐systems, but also to unveil the critical role of this distance for efficient catalysis. A linear correlation was established between photocatalytic activity and the reciprocal of inter active‐site distance; a smaller distance led to higher activity. Vacancies created at selected crystallographic positions of MOFs promoted their photocatalytic efficiency. MOF‐525‐J33 with 15.6 Å inter active‐site distance and 33 % vacancies exhibited unprecedented high turnover frequency of 29.5 h−1 in visible‐light‐driven acceptorless dehydrogenation of tetrahydroquinoline at room temperature. Eng zusammenrücken: Anhand einer Serie Metall‐organischer Gerüste (MOFs) wurde untersucht, welche Rolle der Abstand zwischen aktiven Zentren in biologischen Systemen für die katalytische Aktivität spielt. Das Ergebnis: Die photokatalytische Aktivität verhält sich umgekehrt proportional zum Abstand zwischen den aktiven Zentren.