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 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.
- Authors:
-
- Department of Chemistry, Northwestern University, Evanston, IL 60208-3113,
- Department of Chemistry, Northwestern University, Evanston, IL 60208-3113,, Center for Bio-Inspired Energy Science, Northwestern University, Chicago, IL 60611-3015
- 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. Tue .
"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 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.},
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}
}
https://doi.org/10.1073/pnas.1805625115
Web of Science
Works referenced in this record:
Photovoltaic concepts inspired by coherence effects in photosynthetic systems
journal, December 2016
- Brédas, Jean-Luc; Sargent, Edward H.; Scholes, Gregory D.
- Nature Materials, Vol. 16, Issue 1
Photocatalytic CO 2 Reduction Using Cu(I) Photosensitizers with a Fe(II) Catalyst
journal, March 2016
- Takeda, Hiroyuki; Ohashi, Kenji; Sekine, Akiko
- Journal of the American Chemical Society, Vol. 138, Issue 13
Towards non-blinking colloidal quantum dots
journal, June 2008
- Mahler, Benoit; Spinicelli, Piernicola; Buil, Stéphanie
- Nature Materials, Vol. 7, Issue 8
Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods
journal, August 2014
- Simon, Thomas; Bouchonville, Nicolas; Berr, Maximilian J.
- Nature Materials, Vol. 13, Issue 11
Carbon dots as photosensitisers for solar-driven catalysis
journal, January 2017
- Hutton, Georgina A. M.; Martindale, Benjamin C. M.; Reisner, Erwin
- Chemical Society Reviews, Vol. 46, Issue 20
Semiconductor quantum dot-sensitized rainbow photocathode for effective photoelectrochemical hydrogen generation
journal, October 2017
- Lv, Hongjin; Wang, Congcong; Li, Guocan
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 43
Semiconductor-based Photocatalytic Hydrogen Generation
journal, November 2010
- Chen, Xiaobo; Shen, Shaohua; Guo, Liejin
- Chemical Reviews, Vol. 110, Issue 11
Artificial Photosynthesis: Molecular Systems for Catalytic Water Oxidation
journal, October 2014
- Kärkäs, Markus D.; Verho, Oscar; Johnston, Eric V.
- Chemical Reviews, Vol. 114, Issue 24
Distance-Dependence of Interparticle Energy Transfer in the Near-Infrared within Electrostatic Assemblies of PbS Quantum Dots
journal, April 2017
- Kodaimati, Mohamad S.; Wang, Chen; Chapman, Craig
- ACS Nano, Vol. 11, Issue 5
The photoluminescence spectral profiles of water-soluble aggregates of PbS quantum dots assembled through reversible metal coordination
journal, January 2017
- Wang, Chen; Kodaimati, Mohamad Saeed; Schatz, George C.
- Chemical Communications, Vol. 53, Issue 12
Near-Quantitative Yield for Transfer of Near-Infrared Excitons within Solution-Phase Assemblies of PbS Quantum Dots
journal, September 2016
- Lee, Ki-Ryong; Bettis Homan, Stephanie; Kodaimati, Mohamad
- The Journal of Physical Chemistry C, Vol. 120, Issue 39
Photogeneration of hydrogen from water using CdSe nanocrystals demonstrating the importance of surface exchange
journal, September 2013
- Das, A.; Han, Z.; Haghighi, M. G.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 42
Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst
journal, November 2012
- Han, Z.; Qiu, F.; Eisenberg, R.
- Science, Vol. 338, Issue 6112
Self-Assembled Framework Enhances Electronic Communication of Ultrasmall-Sized Nanoparticles for Exceptional Solar Hydrogen Evolution
journal, March 2017
- Li, Xu-Bing; Gao, Yu-Ji; Wang, Yang
- Journal of the American Chemical Society, Vol. 139, Issue 13
Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water
journal, January 2015
- Das, Amit; Han, Zhiji; Brennessel, William W.
- ACS Catalysis, Vol. 5, Issue 3
Visible-Light Induced Water Detoxification Catalyzed by Pt II Dye Sensitized Titania
journal, September 2008
- Zhao, Wei; Sun, Yali; Castellano, Felix N.
- Journal of the American Chemical Society, Vol. 130, Issue 38
Principles, Efficiency, and Blueprint Character of Solar-Energy Conversion in Photosynthetic Water Oxidation
journal, December 2009
- Dau, Holger; Zaharieva, Ivelina
- Accounts of Chemical Research, Vol. 42, Issue 12
WO 3 -based photocatalysts: morphology control, activity enhancement and multifunctional applications
journal, January 2017
- Dong, Pengyu; Hou, Guihua; Xi, Xinguo
- Environmental Science: Nano, Vol. 4, Issue 3
Efficient and Limiting Reactions in Aqueous Light-Induced Hydrogen Evolution Systems using Molecular Catalysts and Quantum Dots
journal, May 2014
- Gimbert-Suriñach, Carolina; Albero, Josep; Stoll, Thibaut
- Journal of the American Chemical Society, Vol. 136, Issue 21
Light Absorption and Energy Transfer in the Antenna Complexes of Photosynthetic Organisms
journal, March 2016
- Mirkovic, Tihana; Ostroumov, Evgeny E.; Anna, Jessica M.
- Chemical Reviews, Vol. 117, Issue 2
The native architecture of a photosynthetic membrane
journal, August 2004
- Bahatyrova, Svetlana; Frese, Raoul N.; Siebert, C. Alistair
- Nature, Vol. 430, Issue 7003
Energy Transfer in Aqueous Solutions of Oppositely Charged CdSe/ZnS Core/Shell Quantum Dots and in Quantum Dot−Nanogold Assemblies
journal, March 2004
- Wargnier, Richard; Baranov, Alexandre V.; Maslov, Vladimir G.
- Nano Letters, Vol. 4, Issue 3
A Little Coherence in Photosynthetic Light Harvesting
journal, November 2013
- Anna, Jessica M.; Scholes, Gregory D.; van Grondelle, Rienk
- BioScience, Vol. 64, Issue 1
Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO 2 to CO in Water
journal, January 2018
- Lian, Shichen; Kodaimati, Mohamad S.; Weiss, Emily A.
- ACS Nano, Vol. 12, Issue 1
Powering a CO 2 Reduction Catalyst with Visible Light through Multiple Sub-picosecond Electron Transfers from a Quantum Dot
journal, June 2017
- Lian, Shichen; Kodaimati, Mohamad S.; Dolzhnikov, Dmitriy S.
- Journal of the American Chemical Society, Vol. 139, Issue 26
Selective Photocatalytic CO 2 Reduction in Water through Anchoring of a Molecular Ni Catalyst on CdS Nanocrystals
journal, May 2017
- Kuehnel, Moritz F.; Orchard, Katherine L.; Dalle, Kristian E.
- Journal of the American Chemical Society, Vol. 139, Issue 21
Enhanced Photocatalysis of Rhenium(I) Complex by Light-Harvesting Periodic Mesoporous Organosilica
journal, May 2010
- Takeda, Hiroyuki; Ohashi, Masataka; Tani, Takao
- Inorganic Chemistry, Vol. 49, Issue 10
Multiscale model of light harvesting by photosystem II in plants
journal, January 2016
- Amarnath, Kapil; Bennett, Doran I. G.; Schneider, Anna R.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 5
Hydrogen Production by Molecular Photocatalysis
journal, October 2007
- Esswein, Arthur J.; Nocera, Daniel G.
- Chemical Reviews, Vol. 107, Issue 10
Chlorophyll Fluorescence: A Probe of Photosynthesis In Vivo
journal, June 2008
- Baker, Neil R.
- Annual Review of Plant Biology, Vol. 59, Issue 1
An Exceptional Artificial Photocatalyst, Ni h -CdSe/CdS Core/Shell Hybrid, Made In Situ from CdSe Quantum Dots and Nickel Salts for Efficient Hydrogen Evolution
journal, August 2013
- Li, Zhi-Jun; Wang, Jiu-Ju; Li, Xu-Bing
- Advanced Materials, Vol. 25, Issue 45
Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid
journal, April 2016
- Brown, K. A.; Harris, D. F.; Wilker, M. B.
- Science, Vol. 352, Issue 6284
A Place in the Sun for Artificial Photosynthesis?
journal, May 2016
- Su, Jinzhan; Vayssieres, Lionel
- ACS Energy Letters, Vol. 1, Issue 1
Working the Other Way Around: Photocatalytic Water Oxidation Triggered by Reductive Quenching of the Photoexcited Chromophore
journal, January 2015
- Natali, Mirco; Puntoriero, Fausto; Chiorboli, Claudio
- The Journal of Physical Chemistry C, Vol. 119, Issue 5
Direct-Coupling O 2 Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts
journal, August 2011
- Wang, Lee-Ping; Van Voorhis, Troy
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 17
Fuel from Water: The Photochemical Generation of Hydrogen from Water
journal, June 2014
- Han, Zhiji; Eisenberg, Richard
- Accounts of Chemical Research, Vol. 47, Issue 8
ZnSe quantum dots modified with a Ni(cyclam) catalyst for efficient visible-light driven CO 2 reduction in water
journal, January 2018
- Kuehnel, Moritz F.; Sahm, Constantin D.; Neri, Gaia
- Chemical Science, Vol. 9, Issue 9
Charge Carrier Resolved Relaxation of the First Excitonic State in CdSe Quantum Dots Probed with Near-Infrared Transient Absorption Spectroscopy †
journal, November 2010
- McArthur, Eric A.; Morris-Cohen, Adam J.; Knowles, Kathryn E.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
Architecture of the Photosynthetic Oxygen-Evolving Center
journal, March 2004
- Ferreira, K. N.
- Science, Vol. 303, Issue 5665