TY - JOUR
T1 - Powering a CO2 Reduction Catalyst with Visible Light through Multiple Sub-picosecond Electron Transfers from a Quantum Dot
AU - Lian, Shichen
AU - Kodaimati, Mohamad S.
AU - Dolzhnikov, Dmitriy S.
AU - Calzada, Raul
AU - Weiss, Emily A.
N1 - Funding Information:
This work was primarily supported as part of the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award No. DE-SC0001059 (sensitizer synthesis and catalysis studies), and by the National Science Foundation (NSF) under Award No. CHE-1400596 (optical studies).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/7/5
Y1 - 2017/7/5
N2 - Photosensitization of molecular catalysts to reduce CO2 to CO is a sustainable route to storable solar fuels. Crucial to the sensitization process is highly efficient transfer of redox equivalents from sensitizer to catalyst; in systems with molecular sensitizers, this transfer is often slow because it is gated by diffusion-limited collisions between sensitizer and catalyst. This article describes the photosensitization of a meso-tetraphenylporphyrin iron(III) chloride (FeTPP) catalyst by colloidal, heavy metal-free CuInS2/ZnS quantum dots (QDs) to reduce CO2 to CO using 450 nm light. The sensitization efficiency (turnover number per absorbed unit of photon energy) of the QD system is a factor of 18 greater than that of an analogous system with a fac-tris(2-phenylpyridine)iridium sensitizer. This high efficiency originates in ultrafast electron transfer between the QD and FeTPP, enabled by formation of QD/FeTPP complexes. Optical spectroscopy reveals that the electron-transfer processes primarily responsible for the first two sensitization steps (FeIIITPP ? FeIITPP, and FeIITPP ? FeITPP) both occur in <200 fs.
AB - Photosensitization of molecular catalysts to reduce CO2 to CO is a sustainable route to storable solar fuels. Crucial to the sensitization process is highly efficient transfer of redox equivalents from sensitizer to catalyst; in systems with molecular sensitizers, this transfer is often slow because it is gated by diffusion-limited collisions between sensitizer and catalyst. This article describes the photosensitization of a meso-tetraphenylporphyrin iron(III) chloride (FeTPP) catalyst by colloidal, heavy metal-free CuInS2/ZnS quantum dots (QDs) to reduce CO2 to CO using 450 nm light. The sensitization efficiency (turnover number per absorbed unit of photon energy) of the QD system is a factor of 18 greater than that of an analogous system with a fac-tris(2-phenylpyridine)iridium sensitizer. This high efficiency originates in ultrafast electron transfer between the QD and FeTPP, enabled by formation of QD/FeTPP complexes. Optical spectroscopy reveals that the electron-transfer processes primarily responsible for the first two sensitization steps (FeIIITPP ? FeIITPP, and FeIITPP ? FeITPP) both occur in <200 fs.
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U2 - 10.1021/jacs.7b03134
DO - 10.1021/jacs.7b03134
M3 - Article
C2 - 28608682
AN - SCOPUS:85022062949
SN - 0002-7863
VL - 139
SP - 8931
EP - 8938
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 26
ER -