Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies
Abstract
Excitonic energy transfer (EnT) is the mechanism by which natural photosynthetic systems funnel energy from hundreds of antenna pigments to a single reaction center, which allows multielectron redox reactions to proceed with high efficiencies in low-flux natural light. This paper describes the use of electrostatically assembled CdSe quantum dot (QD) aggregates as artificial light harvesting–reaction center units for the photocatalytic reduction of H + to H 2 , where excitons are funneled through EnT from sensitizer QDs (sQDs) to catalyst QDs (cQDs). Upon increasing the sensitizer-to-catalyst ratio in the aggregates from 1:2 to 20:1, the number of excitons delivered to each cQD (via EnT) per excitation of the system increases by a factor of nine. At the optimized sensitizer-to-catalyst ratio of 4:1, the internal quantum efficiency (IQE) of the reaction system is 4.0 ± 0.3%, a factor of 13 greater than the IQE of a sample that is identical except that EnT is suppressed due to the relative core sizes of the sQDs and cQDs. A kinetic model supports the proposed exciton funneling mechanism for enhancement of the catalytic activity.
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1462458
- Alternate Identifier(s):
- OSTI ID: 1540299
- Grant/Contract Number:
- SC0000989
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 33; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kodaimati, Mohamad S., Lian, Shichen, Schatz, George C., and Weiss, Emily A. Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies. United States: N. p., 2018.
Web. doi:10.1073/pnas.1805625115.
Kodaimati, Mohamad S., Lian, Shichen, Schatz, George C., & Weiss, Emily A. Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies. United States. https://doi.org/10.1073/pnas.1805625115
Kodaimati, Mohamad S., Lian, Shichen, Schatz, George C., and Weiss, Emily A. Wed .
"Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies". United States. https://doi.org/10.1073/pnas.1805625115.
@article{osti_1462458,
title = {Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies},
author = {Kodaimati, Mohamad S. and Lian, Shichen and Schatz, George C. and Weiss, Emily A.},
abstractNote = {Excitonic energy transfer (EnT) is the mechanism by which natural photosynthetic systems funnel energy from hundreds of antenna pigments to a single reaction center, which allows multielectron redox reactions to proceed with high efficiencies in low-flux natural light. This paper describes the use of electrostatically assembled CdSe quantum dot (QD) aggregates as artificial light harvesting–reaction center units for the photocatalytic reduction of H + to H 2 , where excitons are funneled through EnT from sensitizer QDs (sQDs) to catalyst QDs (cQDs). Upon increasing the sensitizer-to-catalyst ratio in the aggregates from 1:2 to 20:1, the number of excitons delivered to each cQD (via EnT) per excitation of the system increases by a factor of nine. At the optimized sensitizer-to-catalyst ratio of 4:1, the internal quantum efficiency (IQE) of the reaction system is 4.0 ± 0.3%, a factor of 13 greater than the IQE of a sample that is identical except that EnT is suppressed due to the relative core sizes of the sQDs and cQDs. A kinetic model supports the proposed exciton funneling mechanism for enhancement of the catalytic activity.},
doi = {10.1073/pnas.1805625115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 33,
volume = 115,
place = {United States},
year = {2018},
month = {8}
}
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https://doi.org/10.1073/pnas.1805625115
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