Abstract
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.
Original language | English (US) |
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Pages (from-to) | 98-119 |
Number of pages | 22 |
Journal | Coordination Chemistry Reviews |
Volume | 361 |
DOIs | |
State | Published - Apr 15 2018 |
Funding
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.
Keywords
- Artificial photosynthesis
- CO reduction
- Photoinduced electron transfer
- Radical anions
- Solar fuels
- Transient absorption
- Ultrafast spectroscopy
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry