TY - JOUR
T1 - Photoexcited radical anion super-reductants for solar fuels catalysis
AU - La Porte, Nathan T.
AU - Martinez, Jose F.
AU - Chaudhuri, Subhajyoti
AU - Hedström, Svante
AU - Batista, Victor S.
AU - Wasielewski, Michael R.
N1 - Funding Information:
This work was supported by ANSER, an Energy Frontier Research Center funded by the U.S. DOE under Award No. DE-SC0001059 (experimental and computational work) and by a generous donation from the TomKat foundation (computational work). This publication was made possible by NPRP Grant No. 9-174-2-092 from the Qatar National Research Fund (a member of Qatar Foundation). Benjamin Rudshteyn performed preliminary calculations on the dianion dyad and Dr. Atanu Acharya supplied the pairwise Coulomb-interaction code. We thank Brandon Rugg and Dr. Elias Diesen for helpful discussions regarding the spin statistics of the PDI-Phbpy-Re-Py system discussed in Section 5.1 . For computer resources, we thank Yale HPC, XSEDE, and NERSC.
Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/4/15
Y1 - 2018/4/15
N2 - The catalytic transformation of carbon dioxide into fuels is one of the most important reactions for creating a sustainable, carbon-neutral energy economy. Given that the sun is the only plausible energy source that can accommodate the increased global energy demand without contributing to catastrophic climate change, it makes sense to use solar energy to drive this reaction, ideally using the largest possible portion of the solar spectrum. Over the past several years, we have explored the use of reduced rylenediimide chromophores, which absorb wavelengths ranging into the near-infrared, as strongly reducing photosensitizers capable of photosensitizing Re(diimine)(CO)3L metal centers towards the binding and reduction of CO2. We have explored the effects of varying the binding geometry, donor–acceptor redox potentials, and excitation wavelength on the kinetics of electron transfer from the reduced rylenediimide to the metal center. So far, we have achieved charge-separated lifetimes in electrocatalytically active complexes of 25 ns when illuminated with near-infrared light, and >250 ns when illuminated with blue light.
AB - The catalytic transformation of carbon dioxide into fuels is one of the most important reactions for creating a sustainable, carbon-neutral energy economy. Given that the sun is the only plausible energy source that can accommodate the increased global energy demand without contributing to catastrophic climate change, it makes sense to use solar energy to drive this reaction, ideally using the largest possible portion of the solar spectrum. Over the past several years, we have explored the use of reduced rylenediimide chromophores, which absorb wavelengths ranging into the near-infrared, as strongly reducing photosensitizers capable of photosensitizing Re(diimine)(CO)3L metal centers towards the binding and reduction of CO2. We have explored the effects of varying the binding geometry, donor–acceptor redox potentials, and excitation wavelength on the kinetics of electron transfer from the reduced rylenediimide to the metal center. So far, we have achieved charge-separated lifetimes in electrocatalytically active complexes of 25 ns when illuminated with near-infrared light, and >250 ns when illuminated with blue light.
KW - Artificial photosynthesis
KW - CO reduction
KW - Photoinduced electron transfer
KW - Radical anions
KW - Solar fuels
KW - Transient absorption
KW - Ultrafast spectroscopy
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U2 - 10.1016/j.ccr.2018.01.018
DO - 10.1016/j.ccr.2018.01.018
M3 - Review article
AN - SCOPUS:85044597120
VL - 361
SP - 98
EP - 119
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
SN - 0010-8545
ER -
