Strong Visible-Light-Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis |
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Authors: | Kai-Kai Chen Dr Song Guo Dr Heyuan Liu Prof Xiyou Li Prof Zhi-Ming Zhang Prof Tong-Bu Lu |
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Institution: | 1. MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, Tianjin University of Technology, Tianjin, 300384 China;2. School of Materials Science and Engineering, College of New Energy, China University of Petroleum (East China), Qingdao, Shandong, 266580 China |
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Abstract: | Developing strong visible-light-absorbing (SVLA) earth-abundant photosensitizers (PSs) for significantly improving the utilization of solar energy is highly desirable, yet it remains a great challenge. Herein, we adopt a through-bond energy transfer (TBET) strategy by bridging boron dipyrromethene (Bodipy) and a CuI complex with an electronically conjugated bridge, resulting in the first SVLA CuI PSs ( Cu-2 and Cu-3 ). Cu-3 has an extremely high molar extinction coefficient of 162 260 m −1 cm−1 at 518 nm, over 62 times higher than that of traditional CuI PS ( Cu-1 ). The photooxidation activity of Cu-3 is much greater than that of Cu-1 and noble-metal PSs (Ru(bpy)32+ and Ir(ppy)3+) for both energy- and electron-transfer reactions. Femto- and nanosecond transient absorption and theoretical investigations demonstrate that a “ping-pong” energy-transfer process in Cu-3 involving a forward singlet TBET from Bodipy to the CuI complex and a backward triplet-triplet energy transfer greatly contribute to the long-lived and Bodipy-localized triplet excited state. |
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Keywords: | copper light harvesting oxidation photosensitizers photocatalysis |
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