skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots

Abstract

Quantum confined semiconductor nanocrystals have emerged as a new class of materials for light harvesting and charge separation applications due to the ability to control their properties through rational design of their size, shape and composition. We report here a study of enhancing the quantum yield of methyl viologen (MV 2+) photoreduction using colloidal quasi-type II CdSe/CdS core/shell quantum dots (QDs). The steady-state quantum yield of MV +c radical generation, in the presence of thiols as sacrificial donors, increased monotonically with the CdS shell thickness within the studied thickness regime (0–4.7 CdS monolayers). Using ultrafast transient absorption and time-resolved photoluminescence decay spectroscopy, we found that both the rates of electron transfer from the QD to MV 2+ and the subsequent charge recombination in QD +–MV +c complexes decreased exponentially with the shell thickness, consistent with calculated 1S electron and hole densities at the QD surfaces, respectively. Interestingly, the hole transfer rate remained relatively independent of shell thickness, likely due to a cancellation of the reduction of hole transfer coupling strength with the increased number of hole acceptor ligands on the QD surface at larger shell thickness. As a result, with increasing CdS shell thickness, the charge recombination loss decreases, enhancingmore » the photoreduction quantum efficiency. This novel approach for improving photoreduction quantum efficiency should be applicable to many type II and quasi-type II core/shell quantum dots.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [3];  [2]
  1. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry; Xiamen Univ. (China). College of Chemistry and Chemical Engineering. Dept. of Chemistry. State Key Lab. of Physical Chemistry of Solid Surfaces
  2. Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
  3. Xiamen Univ. (China). College of Chemistry and Chemical Engineering. Dept. of Chemistry. State Key Lab. of Physical Chemistry of Solid Surfaces
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1624935
Grant/Contract Number:  
FG02-07ER15906; AFSR [FA9550-13-1-0020]
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 77 NANOSCIENCE AND NANOTECHNOLOGY; Chemistry

Citation Formats

Jia, Yanyan, Chen, Jinquan, Wu, Kaifeng, Kaledin, Alex, Musaev, Djamaladdin G., Xie, Zhaoxiong, and Lian, Tianquan. Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots. United States: N. p., 2016. Web. doi:10.1039/c6sc00192k.
Jia, Yanyan, Chen, Jinquan, Wu, Kaifeng, Kaledin, Alex, Musaev, Djamaladdin G., Xie, Zhaoxiong, & Lian, Tianquan. Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots. United States. doi:10.1039/c6sc00192k.
Jia, Yanyan, Chen, Jinquan, Wu, Kaifeng, Kaledin, Alex, Musaev, Djamaladdin G., Xie, Zhaoxiong, and Lian, Tianquan. Fri . "Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots". United States. doi:10.1039/c6sc00192k. https://www.osti.gov/servlets/purl/1624935.
@article{osti_1624935,
title = {Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots},
author = {Jia, Yanyan and Chen, Jinquan and Wu, Kaifeng and Kaledin, Alex and Musaev, Djamaladdin G. and Xie, Zhaoxiong and Lian, Tianquan},
abstractNote = {Quantum confined semiconductor nanocrystals have emerged as a new class of materials for light harvesting and charge separation applications due to the ability to control their properties through rational design of their size, shape and composition. We report here a study of enhancing the quantum yield of methyl viologen (MV2+) photoreduction using colloidal quasi-type II CdSe/CdS core/shell quantum dots (QDs). The steady-state quantum yield of MV+c radical generation, in the presence of thiols as sacrificial donors, increased monotonically with the CdS shell thickness within the studied thickness regime (0–4.7 CdS monolayers). Using ultrafast transient absorption and time-resolved photoluminescence decay spectroscopy, we found that both the rates of electron transfer from the QD to MV2+ and the subsequent charge recombination in QD+–MV+c complexes decreased exponentially with the shell thickness, consistent with calculated 1S electron and hole densities at the QD surfaces, respectively. Interestingly, the hole transfer rate remained relatively independent of shell thickness, likely due to a cancellation of the reduction of hole transfer coupling strength with the increased number of hole acceptor ligands on the QD surface at larger shell thickness. As a result, with increasing CdS shell thickness, the charge recombination loss decreases, enhancing the photoreduction quantum efficiency. This novel approach for improving photoreduction quantum efficiency should be applicable to many type II and quasi-type II core/shell quantum dots.},
doi = {10.1039/c6sc00192k},
journal = {Chemical Science},
issn = {2041-6520},
number = 7,
volume = 7,
place = {United States},
year = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Hole Removal Rate Limits Photodriven H 2 Generation Efficiency in CdS-Pt and CdSe/CdS-Pt Semiconductor Nanorod–Metal Tip Heterostructures
journal, May 2014

  • Wu, Kaifeng; Chen, Zheyuan; Lv, Hongjin
  • Journal of the American Chemical Society, Vol. 136, Issue 21
  • DOI: 10.1021/ja5023893

Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals
journal, July 2003

  • Yu, W. William; Qu, Lianhua; Guo, Wenzhuo
  • Chemistry of Materials, Vol. 15, Issue 14, p. 2854-2860
  • DOI: 10.1021/cm034081k

Auger-Assisted Electron Transfer from Photoexcited Semiconductor Quantum Dots
journal, February 2014

  • Zhu, Haiming; Yang, Ye; Hyeon-Deuk, Kim
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl4041687

Hydrogen evolution from water induced by visible light mediated by redox catalysis
journal, October 1979

  • Kiwi, John; Grätzel, Michael
  • Nature, Vol. 281, Issue 5733
  • DOI: 10.1038/281657a0

Hot-Electron Transfer from Semiconductor Nanocrystals
journal, June 2010


Wave Function Engineering for Ultrafast Charge Separation and Slow Charge Recombination in Type II Core/Shell Quantum Dots
journal, June 2011

  • Zhu, Haiming; Song, Nianhui; Lian, Tianquan
  • Journal of the American Chemical Society, Vol. 133, Issue 22
  • DOI: 10.1021/ja202752s

Electron-transfer communication between a redox polymer matrix and an immobilized enzyme: activity of nitrate reductase in a viologen-acrylamide copolymer
journal, August 1990

  • Willner, Itamar; Riklin, Azalia; Lapidot, Noa
  • Journal of the American Chemical Society, Vol. 112, Issue 17
  • DOI: 10.1021/ja00173a065

Beyond Band Alignment: Hole Localization Driven Formation of Three Spatially Separated Long-Lived Exciton States in CdSe/CdS Nanorods
journal, July 2013

  • Wu, Kaifeng; Rodríguez-Córdoba, William E.; Liu, Zheng
  • ACS Nano, Vol. 7, Issue 8
  • DOI: 10.1021/nn402597p

Poisson-Distributed Electron-Transfer Dynamics from Single Quantum Dots to C60 Molecules
journal, December 2010

  • Song, Nianhui; Zhu, Haiming; Jin, Shengye
  • ACS Nano, Vol. 5, Issue 1
  • DOI: 10.1021/nn1028828

Distance-Dependent Electron Transfer in DNA Hairpins
journal, August 1997


Multiple Exciton Collection in a Sensitized Photovoltaic System
journal, September 2010


Peak External Photocurrent Quantum Efficiency Exceeding 100% via MEG in a Quantum Dot Solar Cell
journal, December 2011


Efficiency of Hole Transfer from Photoexcited Quantum Dots to Covalently Linked Molecular Species
journal, January 2015

  • Ding, Tina X.; Olshansky, Jacob H.; Leone, Stephen R.
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512278a

Hole scavenger redox potentials determine quantum efficiency and stability of Pt-decorated CdS nanorods for photocatalytic hydrogen generation
journal, May 2012

  • Berr, Maximilian J.; Wagner, Peter; Fischbach, Stefan
  • Applied Physics Letters, Vol. 100, Issue 22
  • DOI: 10.1063/1.4723575

Near Unity Quantum Yield of Light-Driven Redox Mediator Reduction and Efficient H 2 Generation Using Colloidal Nanorod Heterostructures
journal, July 2012

  • Zhu, Haiming; Song, Nianhui; Lv, Hongjin
  • Journal of the American Chemical Society, Vol. 134, Issue 28
  • DOI: 10.1021/ja303698e

Efficient hot-electron transfer by a plasmon-induced interfacial charge-transfer transition
journal, August 2015


Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst
journal, November 2012


Mapping the Optical Properties of CdSe/CdS Heterostructure Nanocrystals: The Effects of Core Size and Shell Thickness
journal, October 2009

  • van Embden, Joel; Jasieniak, Jacek; Mulvaney, Paul
  • Journal of the American Chemical Society, Vol. 131, Issue 40
  • DOI: 10.1021/ja9030209

Alkanethiolate Gold Cluster Molecules with Core Diameters from 1.5 to 5.2 nm:  Core and Monolayer Properties as a Function of Core Size
journal, January 1998

  • Hostetler, Michael J.; Wingate, Julia E.; Zhong, Chuan-Jian
  • Langmuir, Vol. 14, Issue 1
  • DOI: 10.1021/la970588w

Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology
journal, April 2005

  • Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.
  • Chemical Reviews, Vol. 105, Issue 4
  • DOI: 10.1021/cr0300789

Controlling Charge Separation and Recombination Rates in CdSe/ZnS Type I Core−Shell Quantum Dots by Shell Thicknesses
journal, October 2010

  • Zhu, Haiming; Song, Nianhui; Lian, Tianquan
  • Journal of the American Chemical Society, Vol. 132, Issue 42
  • DOI: 10.1021/ja106710m

Suppressed Auger Recombination in “Giant” Nanocrystals Boosts Optical Gain Performance
journal, October 2009

  • García-Santamaría, Florencio; Chen, Yongfen; Vela, Javier
  • Nano Letters, Vol. 9, Issue 10
  • DOI: 10.1021/nl901681d

Size dependence of exciton fine structure in CdSe quantum dots
journal, June 1996


Large-Scale Synthesis of Nearly Monodisperse CdSe/CdS Core/Shell Nanocrystals Using Air-Stable Reagents via Successive Ion Layer Adsorption and Reaction
journal, October 2003

  • Li, J. Jack; Wang, Y. Andrew; Guo, Wenzhuo
  • Journal of the American Chemical Society, Vol. 125, Issue 41, p. 12567-12575
  • DOI: 10.1021/ja0363563

Simultaneous Determination of the Adsorption Constant and the Photoinduced Electron Transfer Rate for a Cds Quantum Dot–Viologen Complex
journal, July 2011

  • Morris-Cohen, Adam J.; Frederick, Matthew T.; Cass, Laura C.
  • Journal of the American Chemical Society, Vol. 133, Issue 26
  • DOI: 10.1021/ja2010237

Measurement of the extinction coefficient of the methyl viologen cation radical and the efficiency of its formation by semiconductor photocatalysis
journal, July 1982

  • Watanabe, Tadashi; Honda, Kenichi
  • The Journal of Physical Chemistry, Vol. 86, Issue 14
  • DOI: 10.1021/j100211a014

The Effect of the Charge-Separating Interface on Exciton Dynamics in Photocatalytic Colloidal Heteronanocrystals
journal, August 2012

  • O’Connor, Timothy; Panov, Maxim S.; Mereshchenko, Andrey
  • ACS Nano, Vol. 6, Issue 9
  • DOI: 10.1021/nn302810y

Ultrafast Electronic Delocalization in CdSe/CdS Quantum Rod Heterostructures
journal, November 2011

  • Smith, E. Ryan; Luther, Joseph M.; Johnson, Justin C.
  • Nano Letters, Vol. 11, Issue 11
  • DOI: 10.1021/nl202869z

The Role of Hole Localization in Sacrificial Hydrogen Production by Semiconductor–Metal Heterostructured Nanocrystals
journal, July 2011

  • Acharya, Krishna P.; Khnayzer, Rony S.; O’Connor, Timothy
  • Nano Letters, Vol. 11, Issue 7
  • DOI: 10.1021/nl201388c

Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals
journal, May 2007


Photoelectrochemical pumping of enzymatic CO2 reduction
journal, May 1984

  • Parkinson, Bruce A.; Weaver, Paul F.
  • Nature, Vol. 309, Issue 5964
  • DOI: 10.1038/309148a0

Ultrafast exciton quenching by energy and electron transfer in colloidal CdSe nanosheet–Pt heterostructures
journal, January 2015

  • Wu, Kaifeng; Li, Qiuyang; Du, Yongling
  • Chemical Science, Vol. 6, Issue 2
  • DOI: 10.1039/C4SC02994A

Ultrafine and specific catalysts affording efficient hydrogen evolution from water under visible light illumination
journal, June 1981

  • Brugger, Pierre Alain; Cuendet, Pierre; Graetzel, Michael
  • Journal of the American Chemical Society, Vol. 103, Issue 11
  • DOI: 10.1021/ja00401a002

(CdSe)ZnS Core−Shell Quantum Dots: Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites
journal, November 1997

  • Dabbousi, B. O.; Rodriguez-Viejo, J.; Mikulec, F. V.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 46, p. 9463-9475
  • DOI: 10.1021/jp971091y

Wave Function Engineering for Efficient Extraction of up to Nineteen Electrons from One CdSe/CdS Quasi-Type II Quantum Dot
journal, February 2012

  • Zhu, Haiming; Song, Nianhui; Rodríguez-Córdoba, William
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja210312s

Synthesis and Characterization of Strongly Luminescing ZnS-Capped CdSe Nanocrystals
journal, January 1996

  • Hines, Margaret A.; Guyot-Sionnest, Philippe
  • The Journal of Physical Chemistry, Vol. 100, Issue 2, p. 468-471
  • DOI: 10.1021/jp9530562

Multiple Exciton Dissociation in CdSe Quantum Dots by Ultrafast Electron Transfer to Adsorbed Methylene Blue
journal, April 2010

  • Huang, Jier; Huang, Zhuangqun; Yang, Ye
  • Journal of the American Chemical Society, Vol. 132, Issue 13
  • DOI: 10.1021/ja100106z

Multiexciton Annihilation and Dissociation in Quantum Confined Semiconductor Nanocrystals
journal, November 2012

  • Zhu, Haiming; Yang, Ye; Lian, Tianquan
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300202d

Breakdown of Volume Scaling in Auger Recombination in CdSe/CdS Heteronanocrystals: The Role of the Core−Shell Interface
journal, February 2011

  • García-Santamaría, Florencio; Brovelli, Sergio; Viswanatha, Ranjani
  • Nano Letters, Vol. 11, Issue 2
  • DOI: 10.1021/nl103801e

Ultrafast Charge Separation in Multiexcited CdSe Quantum Dots Mediated by Adsorbed Electron Acceptors
journal, February 2009

  • Matylitsky, Victor V.; Dworak, Lars; Breus, Vladimir V.
  • Journal of the American Chemical Society, Vol. 131, Issue 7
  • DOI: 10.1021/ja808084y

Ultrafast Electron Transfer at the Molecule-Semiconductor Nanoparticle Interface
journal, May 2005