Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications.
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.
Department of Chemistry, Marquette University , Milwaukee, Wisconsin 53201, United States.
Brian
B
Pattengale
Department of Chemistry, Marquette University , Milwaukee, Wisconsin 53201, United States.
Sizhuo
S
Yang
Department of Chemistry, Marquette University , Milwaukee, Wisconsin 53201, United States.
John
J
Ludwig
Department of Chemistry, Marquette University , Milwaukee, Wisconsin 53201, United States.
Zhuangqun
Z
Huang
X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60349, United States.
Xiaoyi
X
Zhang
Department of Chemistry, Marquette University , Milwaukee, Wisconsin 53201, United States.
Jier
J
Huang