Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

作者：Brian Pattengale, Sizhuo Yang, John Ludwig, Zhuangqun Huang, Xiaoyi Zhang, Jier Huang · 发表于：Journal of the American Chemical Society · 年份：2016 · DOI：10.1021/jacs.6b04615 · 被引用次数：215 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Magnetism in coordination complexes、Advanced Nanomaterials in Catalysis

Zeolitic imidazolate frameworks (ZIFs) have emerged as a novel class of porous metal-organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV-vis-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge-separated (CS) state with ligand-to-metal charge-transfer character using XTA. The surprisingly long-lived CS state, together with its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion.