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Title: 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.

Authors:
; ; ORCiD logo; ORCiD logo
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.
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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. doi:10.1073/pnas.1805625115.
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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. doi:10.1073/pnas.1805625115.
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@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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DOI: 10.1073/pnas.1805625115
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