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Title: Energy transfer-enhanced photocatalytic reduction of protons within quantum dot light-harvesting–catalyst assemblies

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Department of Chemistry, Northwestern University, Evanston, IL 60208-3113,
  2. Department of Chemistry, Northwestern University, Evanston, IL 60208-3113,, Center for Bio-Inspired Energy Science, Northwestern University, Chicago, IL 60611-3015
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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 H2, 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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0000989
OSTI ID:
1462458
Alternate ID(s):
OSTI ID: 1540299
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 115 Journal Issue: 33; ISSN 0027-8424
Publisher:
Proceedings of the National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 50 works
Citation information provided by
Web of Science

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