Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots Using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability
Abstract
This article describes a procedure for transferring colloidal CdS and CdSe quantum dots (QDs) from organic solvents to water by exchanging their native hydrophobic ligands for phosphonopropionic acid (PPA) ligands, which bind to the QD surface through the phosphonate group. This method, which uses dimethylformamide as an intermediate transfer solvent, was developed in order to produce high-quality water soluble QDs with neither a sulfur-containing ligand nor a polymer encapsulation layer, both of which have disadvantages in applications of QDs to photocatalysis and biological imaging. CdS (CdSe) QDs were transferred to water with a 43% (48%) yield using PPA. The photoluminescence (PL) quantum yield for PPA-capped CdSe QDs is larger than that for QDs capped with the analogous sulfur-containing ligand, mercaptopropionic acid (MPA), by a factor of four at pH 7, and by up to a factor of 100 under basic conditions. The MPA ligands within MPA-capped QDs oxidize at Eox ~ +1.7 V vs. SCE, whereas cyclic voltammograms of PPA-capped QDs show no discerible oxidation peaks at applied potentials up to +2.5 V vs. SCE. The PPA-capped QDs are chemically and colloidally stable for at least five days in the dark, even in the presence of O2, and are stablemore »
- Authors:
-
- Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 1388169
- Grant/Contract Number:
- SC0001059
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 28; Journal Issue: 18; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Calzada, Raul, Thompson, Christopher M., Westmoreland, Dana E., Edme, Kedy, and Weiss, Emily A. Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots Using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability. United States: N. p., 2016.
Web. doi:10.1021/acs.chemmater.6b03106.
Calzada, Raul, Thompson, Christopher M., Westmoreland, Dana E., Edme, Kedy, & Weiss, Emily A. Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots Using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability. United States. https://doi.org/10.1021/acs.chemmater.6b03106
Calzada, Raul, Thompson, Christopher M., Westmoreland, Dana E., Edme, Kedy, and Weiss, Emily A. 2016.
"Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots Using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability". United States. https://doi.org/10.1021/acs.chemmater.6b03106. https://www.osti.gov/servlets/purl/1388169.
@article{osti_1388169,
title = {Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots Using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability},
author = {Calzada, Raul and Thompson, Christopher M. and Westmoreland, Dana E. and Edme, Kedy and Weiss, Emily A.},
abstractNote = {This article describes a procedure for transferring colloidal CdS and CdSe quantum dots (QDs) from organic solvents to water by exchanging their native hydrophobic ligands for phosphonopropionic acid (PPA) ligands, which bind to the QD surface through the phosphonate group. This method, which uses dimethylformamide as an intermediate transfer solvent, was developed in order to produce high-quality water soluble QDs with neither a sulfur-containing ligand nor a polymer encapsulation layer, both of which have disadvantages in applications of QDs to photocatalysis and biological imaging. CdS (CdSe) QDs were transferred to water with a 43% (48%) yield using PPA. The photoluminescence (PL) quantum yield for PPA-capped CdSe QDs is larger than that for QDs capped with the analogous sulfur-containing ligand, mercaptopropionic acid (MPA), by a factor of four at pH 7, and by up to a factor of 100 under basic conditions. The MPA ligands within MPA-capped QDs oxidize at Eox ~ +1.7 V vs. SCE, whereas cyclic voltammograms of PPA-capped QDs show no discerible oxidation peaks at applied potentials up to +2.5 V vs. SCE. The PPA-capped QDs are chemically and colloidally stable for at least five days in the dark, even in the presence of O2, and are stable when continuously illuminated for five days, when oxygen is excluded and a sacrificial reductant is present to capture photogenerated holes.},
doi = {10.1021/acs.chemmater.6b03106},
url = {https://www.osti.gov/biblio/1388169},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 18,
volume = 28,
place = {United States},
year = {Fri Aug 26 00:00:00 EDT 2016},
month = {Fri Aug 26 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Biocompatible fluorescent nanocrystals for immunolabeling of membrane proteins and cells
journal, January 2004
- Sukhanova, Alyona; Devy, Jérôme; Venteo, Lydie
- Analytical Biochemistry, Vol. 324, Issue 1
Targeting Cell Surface Receptors with Ligand-Conjugated Nanocrystals
journal, May 2002
- Rosenthal, Sandra J.; Tomlinson, Ian; Adkins, Erika M.
- Journal of the American Chemical Society, Vol. 124, Issue 17
In Vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles
journal, November 2002
- Dubertret, B.
- Science, Vol. 298, Issue 5599
Quantum Dot Bioconjugates for Ultrasensitive Nonisotopic Detection
journal, September 1998
- Chan, Warren C. W.; Nie, Shuming
- Science, Vol. 281, Issue 5385, p. 2016-2018
Semiconductor Nanocrystals as Fluorescent Biological Labels
patent, September 1998
- Bruchez Jr., Marcel; Moronne, Mario Moronne; Gin, Peter Gin
- Science, Vol. 281, Issue 5385, p. 2013-2016
Semiconductor quantum dots and metal nanoparticles: syntheses, optical properties, and biological applications
journal, June 2008
- Biju, Vasudevanpillai; Itoh, Tamitake; Anas, Abdulaziz
- Analytical and Bioanalytical Chemistry, Vol. 391, Issue 7
Nanocrystal targeting in vivo
journal, September 2002
- Akerman, M. E.; Chan, W. C. W.; Laakkonen, P.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue 20, p. 12617-12621
Water-soluble quantum dots for biomedical applications
journal, September 2006
- Yu, William W.; Chang, Emmanuel; Drezek, Rebekah
- Biochemical and Biophysical Research Communications, Vol. 348, Issue 3
Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot
journal, January 2016
- Jensen, Stephen C.; Bettis Homan, Stephanie; Weiss, Emily A.
- Journal of the American Chemical Society, Vol. 138, Issue 5
Semiconductor-based Photocatalytic Hydrogen Generation
journal, November 2010
- Chen, Xiaobo; Shen, Shaohua; Guo, Liejin
- Chemical Reviews, Vol. 110, Issue 11
Electrostatically Assembled CdS-Co 3 O 4 Nanostructures for Photo-assisted Water Oxidation and Photocatalytic Reduction of Dye Molecules
journal, September 2014
- Yehezkeli, Omer; de Oliveira, Débora R. B.; Cha, Jennifer N.
- Small, Vol. 11, Issue 6
Semiconductors for Photoelectrolysis
journal, August 1978
- Harris, L. A.; Wilson, R. H.
- Annual Review of Materials Science, Vol. 8, Issue 1, p. 99-134
Direct Evidence of Active-Site Reduction and Photodriven Catalysis in Sensitized Hydrogenase Assemblies
journal, June 2012
- Greene, Brandon L.; Joseph, Crisjoe A.; Maroney, Michael J.
- Journal of the American Chemical Society, Vol. 134, Issue 27
Controlled Assembly of Hydrogenase-CdTe Nanocrystal Hybrids for Solar Hydrogen Production
journal, July 2010
- Brown, Katherine A.; Dayal, Smita; Ai, Xin
- Journal of the American Chemical Society, Vol. 132, Issue 28
Characterization of Photochemical Processes for H 2 Production by CdS Nanorod–[FeFe] Hydrogenase Complexes
journal, March 2012
- Brown, Katherine A.; Wilker, Molly B.; Boehm, Marko
- Journal of the American Chemical Society, Vol. 134, Issue 12
Water-Soluble Quantum Dots for Multiphoton Fluorescence Imaging in Vivo
journal, May 2003
- Larson, Daniel R.; Zipfel, Warren R.; Williams, Rebecca M.
- Science, Vol. 300, Issue 5624, p. 1434-1436
Polyethylene glycol-based bidentate ligands to enhance quantum dot and gold nanoparticle stability in biological media
journal, March 2009
- Mei, Bing C.; Susumu, Kimihiro; Medintz, Igor L.
- Nature Protocols, Vol. 4, Issue 3
Synthesis of surface ligands to prepare hydrophilic and biologically compatible quantum dots
conference, April 2005
- Uyeda, H. T.; Medintz, Igor L.; Mattoussi, Hedi
- Biomedical Optics 2005, SPIE Proceedings
Design of Biotin-Functionalized Luminescent Quantum Dots
journal, January 2007
- Susumu, Kimihiro; Uyeda, H. Tetsuo; Medintz, Igor L.
- Journal of Biomedicine and Biotechnology, Vol. 2007
Multidentate Zwitterionic Ligands Provide Compact and Highly Biocompatible Quantum Dots
journal, September 2013
- Zhan, Naiqian; Palui, Goutam; Safi, Malak
- Journal of the American Chemical Society, Vol. 135, Issue 37
Semiconductor Quantum Dots for Bioanalysis
journal, September 2008
- Gill, Ron; Zayats, Maya; Willner, Itamar
- Angewandte Chemie International Edition, Vol. 47, Issue 40
Small GSH-Capped CuInS 2 Quantum Dots: MPA-Assisted Aqueous Phase Transfer and Bioimaging Applications
journal, August 2015
- Zhao, Chuanzhen; Bai, Zelong; Liu, Xiangyou
- ACS Applied Materials & Interfaces, Vol. 7, Issue 32
Synthesis of Compact Multidentate Ligands to Prepare Stable Hydrophilic Quantum Dot Fluorophores
journal, March 2005
- Uyeda, H. Tetsuo; Medintz, Igor L.; Jaiswal, Jyoti K.
- Journal of the American Chemical Society, Vol. 127, Issue 11
Preparation of compact biocompatible quantum dots using multicoordinating molecular-scale ligands based on a zwitterionic hydrophilic motif and lipoic acid anchors
journal, May 2015
- Zhan, Naiqian; Palui, Goutam; Mattoussi, Hedi
- Nature Protocols, Vol. 10, Issue 6
Compact Cysteine-Coated CdSe(ZnCdS) Quantum Dots for in Vivo Applications
journal, November 2007
- Liu, Wenhao; Choi, Hak Soo; Zimmer, John P.
- Journal of the American Chemical Society, Vol. 129, Issue 47
The Effects of Chemisorption on the Luminescence of CdSe Quantum Dots
journal, March 2006
- Bullen, C.; Mulvaney, P.
- Langmuir, Vol. 22, Issue 7
Ligand Effects on Optical Properties of CdSe Nanocrystals
journal, April 2005
- Kalyuzhny, Gregory; Murray, Royce W.
- The Journal of Physical Chemistry B, Vol. 109, Issue 15
The Role of Ligands in Determining the Exciton Relaxation Dynamics in Semiconductor Quantum Dots
journal, April 2014
- Peterson, Mark D.; Cass, Laura C.; Harris, Rachel D.
- Annual Review of Physical Chemistry, Vol. 65, Issue 1
Recent Advances in Quantum Dot Surface Chemistry
journal, February 2014
- Hines, Douglas A.; Kamat, Prashant V.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 5
Tuning the Emission of CdSe Quantum Dots by Controlled Trap Enhancement
journal, July 2010
- Baker, David R.; Kamat, Prashant V.
- Langmuir, Vol. 26, Issue 13
Thiols and Disulfides on the Au(111) Surface: The Headgroup−Gold Interaction
journal, April 2000
- Grönbeck, Henrik; Curioni, Alessandro; Andreoni, Wanda
- Journal of the American Chemical Society, Vol. 122, Issue 16
Synthesis and Optical Properties of Thiol Functionalized CdSe/ZnS (Core/Shell) Quantum Dots by Ligand Exchange
journal, January 2014
- Zhu, Huaping; Hu, Michael Z.; Shao, Lei
- Journal of Nanomaterials, Vol. 2014
Photochemical Instability of CdSe Nanocrystals Coated by Hydrophilic Thiols
journal, September 2001
- Aldana, Jose; Wang, Y. Andrew; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 123, Issue 36
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
Surface-Tunable Photoluminescence from Block Copolymer-Stabilized Cadmium Sulfide Quantum Dots
journal, December 2004
- Wang, C. -W.; Moffitt, M. G.
- Langmuir, Vol. 20, Issue 26
Hydrophobic Nanocrystals Coated with an Amphiphilic Polymer Shell: A General Route to Water Soluble Nanocrystals
journal, April 2004
- Pellegrino, Teresa; Manna, Liberato; Kudera, Stefan
- Nano Letters, Vol. 4, Issue 4, p. 703-707
Design of an Amphiphilic Polymer for Nanoparticle Coating and Functionalization
journal, March 2008
- Lin, Cheng-An J.; Sperling, Ralph A.; Li, Jimmy K.
- Small, Vol. 4, Issue 3
Synthesis and Properties of Biocompatible Water-Soluble Silica-Coated CdSe/ZnS Semiconductor Quantum Dots †
journal, September 2001
- Gerion, Daniele; Pinaud, Fabien; Williams, Shara C.
- The Journal of Physical Chemistry B, Vol. 105, Issue 37
Single Quantum Dots in Spherical Silica Particles
journal, October 2004
- Nann, Thomas; Mulvaney, Paul
- Angewandte Chemie International Edition, Vol. 43, Issue 40
Binding of Phosphonic Acids to CdSe Quantum Dots: A Solution NMR Study
journal, January 2011
- Gomes, Raquel; Hassinen, Antti; Szczygiel, Agnieszka
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 3
Correlation of CdS Nanocrystal Formation with Elemental Sulfur Activation and Its Implication in Synthetic Development
journal, November 2011
- Li, Zheng; Ji, Yijing; Xie, Renguo
- Journal of the American Chemical Society, Vol. 133, Issue 43
Formation of High-Quality CdS and Other II-VI Semiconductor Nanocrystals in Noncoordinating Solvents: Tunable Reactivity of Monomers
journal, July 2002
- Yu, W. William; Peng, Xiaogang
- Angewandte Chemie International Edition, Vol. 41, Issue 13
Synthesis of Metal-Selenide Nanocrystals Using Selenium Dioxide as the Selenium Precursor
journal, October 2008
- Chen, Ou; Chen, Xian; Yang, Yongan
- Angewandte Chemie International Edition, Vol. 47, Issue 45
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
The Chemical Environments of Oleate Species within Samples of Oleate-Coated PbS Quantum Dots
journal, July 2013
- Cass, Laura C.; Malicki, Michał; Weiss, Emily A.
- Analytical Chemistry, Vol. 85, Issue 14
Crystal Structure Control of Zinc-Blende CdSe/CdS Core/Shell Nanocrystals: Synthesis and Structure-Dependent Optical Properties
journal, November 2012
- Nan, Wennuan; Niu, Yuan; Qin, Haiyan
- Journal of the American Chemical Society, Vol. 134, Issue 48
(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
Epitaxial Growth of Highly Luminescent CdSe/CdS Core/Shell Nanocrystals with Photostability and Electronic Accessibility
journal, July 1997
- Peng, Xiaogang; Schlamp, Michael C.; Kadavanich, Andreas V.
- Journal of the American Chemical Society, Vol. 119, Issue 30, p. 7019-7029
Electron and hole relaxation pathways in semiconductor quantum dots
journal, November 1999
- Klimov, V. I.; McBranch, D. W.; Leatherdale, C. A.
- Physical Review B, Vol. 60, Issue 19
Colloidal Quantum Dot Optoelectronics and Photovoltaics
book, November 2013
- Konstantatos, Gerasimos; Sargent, Edward H.
Time resolved and temperature dependence of the radiative properties of thiol-capped CdS nanoparticles films
journal, January 2014
- Bel Haj Mohamed, N.; Haouari, M.; Zaaboub, Z.
- Journal of Nanoparticle Research, Vol. 16, Issue 2
Dependence of the Band Gap of CdSe Quantum Dots on the Surface Coverage and Binding Mode of an Exciton-Delocalizing Ligand, Methylthiophenolate
journal, August 2015
- Amin, Victor A.; Aruda, Kenneth O.; Lau, Bryan
- The Journal of Physical Chemistry C, Vol. 119, Issue 33
Description of the Adsorption and Exciton Delocalizing Properties of p -Substituted Thiophenols on CdSe Quantum Dots
journal, March 2016
- Aruda, Kenneth O.; Amin, Victor A.; Thompson, Christopher M.
- Langmuir, Vol. 32, Issue 14
Direct Electrochemical Oxidation of Disulfides at Anodically Pretreated Boron-Doped Diamond Electrodes
journal, April 2003
- Terashima, C.; Rao, Tata N.; Sarada, B. V.
- Analytical Chemistry, Vol. 75, Issue 7
Size selective photoetching of nanocrystalline CdS particles
journal, May 1997
- van Dijken, A.; Vanmaekelbergh, D.; Meijerink, A.
- Chemical Physics Letters, Vol. 269, Issue 5-6
Primary Reactions in the Photocorrosion of CdSe Through Photocapacitance Measurements
journal, January 1991
- Allongue, Ph.
- Journal of The Electrochemical Society, Vol. 138, Issue 1
Surface State Analysis of Photobrightening in CdSe Nanocrystal Thin Films
journal, November 2003
- Asami, Harumi; Abe, Yoshimi; Ohtsu, Takeshi
- The Journal of Physical Chemistry B, Vol. 107, Issue 46
Multicolor Luminescence Patterning by Photoactivation of Semiconductor Nanoparticle Films
journal, March 2003
- Wang, Ying; Tang, Zhiyong; Correa-Duarte, Miguel A.
- Journal of the American Chemical Society, Vol. 125, Issue 10
Works referencing / citing this record:
Colloidally Stable CdS Quantum Dots in Water with Electrostatically Stabilized Weak‐Binding, Sulfur‐Free Ligands
journal, October 2019
- Arcudi, Francesca; Westmoreland, Dana Emily; Weiss, Emily Allyn
- Chemistry – A European Journal, Vol. 25, Issue 63
High-density quantum dots composites and its photolithographic patterning applications
journal, December 2018
- Lee, Seonwoo; Lee, Changhee
- Polymers for Advanced Technologies, Vol. 30, Issue 3
The SALSAC approach: comparing the reactivity of solvent-dispersed nanoparticles with nanoparticulate surfaces
journal, January 2020
- Freimann, Sven A.; Zare, Davood; Housecroft, Catherine E.
- Nanoscale Advances, Vol. 2, Issue 2
pH-Dependent structure of water-exposed surfaces of CdSe quantum dots
journal, January 2019
- Westmoreland, Dana E.; Nap, Rikkert J.; Arcudi, Francesca
- Chemical Communications, Vol. 55, Issue 38
An Efficient Method for the Surface Functionalization of Luminescent Quantum Dots with Lipoic Acid Based Ligands: An Efficient Method for the Surface Functionalization of Luminescent Quantum Dots with Lipoic Acid Based Ligands
journal, October 2017
- La Rosa, Marcello; Avellini, Tommaso; Lincheneau, Christophe
- European Journal of Inorganic Chemistry, Vol. 2017, Issue 44
The SALSAC Approach: Comparing the reactivity of solventdispersed nanoparticles with nanoparticulate surfaces
text, January 2020
- Freimann, Sven; Zare, Davood; Housecroft, Catherine E.
- Royal Society of Chemistry
An Efficient Method for the Surface Functionalization of Luminescent Quantum Dots with Lipoic Acid Based Ligands
text, January 2017
- La Rosa, Marcello; Avellini, Tommaso; Lincheneau, Christophe
- Wiley