In situ spectroscopic characterization of a solution-phase X-type ligand exchange at colloidal lead sulphide quantum dot surfaces

Kroupa, Daniel M.; Anderson, Nicholas C.; Castaneda, Chloe V.; Nozik, Arthur J.; Beard, Matt C.

doi:10.1039/C6CC08114B

Title: In situ spectroscopic characterization of a solution-phase X-type ligand exchange at colloidal lead sulphide quantum dot surfaces

Journal Article · Mon Nov 07 00:00:00 EST 2016 · ChemComm

DOI:https://doi.org/10.1039/C6CC08114B· OSTI ID:1334589

Kroupa, Daniel M. ^[1]; Anderson, Nicholas C. ^[2]; Castaneda, Chloe V. ^[2]; Nozik, Arthur J. ^[1]; Beard, Matt C. ^[2]

National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Here, we employed quantitative NMR spectroscopy and spectrophotometric absorbance titration to study a quantum dot X-type ligand exchange reaction. We find that the exchange is highly cooperative, where at low extents of exchange the change in free energy of the reaction, ΔG_XC, is ~11 kJ mol^–1 while at higher extents of exchange ΔG_XC saturates to ~–4 kJ mol^–1. A modified Fowler binding isotherm is developed to describe the reaction.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1334589

Report Number(s):: NREL/JA-5900-67253; CHCOFS

Journal Information:: ChemComm, Vol. 52, Issue 96; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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References (13)

Ligand Adsorption/Desorption on Sterically Stabilized InP Colloidal Nanocrystals: Observation and Thermodynamic Analysis Moreels, Iwan; Martins, Jose C.; Hens, Zeger ChemPhysChem, Vol. 7, Issue 5 https://doi.org/10.1002/cphc.200500659	journal	May 2006
The surface science of nanocrystals Boles, Michael A.; Ling, Daishun; Hyeon, Taeghwan Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4526	journal	January 2016
Size-Dependent Optical Properties of Colloidal PbS Quantum Dots Moreels, Iwan; Lambert, Karel; Smeets, Dries ACS Nano, Vol. 3, Issue 10 https://doi.org/10.1021/nn900863a	journal	September 2009
Quantifying Ligand Exchange Reactions at CdSe Nanocrystal Surfaces Knauf, Robin R.; Lennox, J. Christian; Dempsey, Jillian L. Chemistry of Materials, Vol. 28, Issue 13 https://doi.org/10.1021/acs.chemmater.6b01827	journal	June 2016
Relaxation of Exciton Confinement in CdSe Quantum Dots by Modification with a Conjugated Dithiocarbamate Ligand Frederick, Matthew T.; Weiss, Emily A. ACS Nano, Vol. 4, Issue 6 https://doi.org/10.1021/nn1007435	journal	May 2010
Utilizing Self-Exchange To Address the Binding of Carboxylic Acid Ligands to CdSe Quantum Dots Fritzinger, Bernd; Capek, Richard K.; Lambert, Karel Journal of the American Chemical Society, Vol. 132, Issue 29 https://doi.org/10.1021/ja104351q	journal	July 2010
PbSe Quantum Dot Field-Effect Transistors with Air-Stable Electron Mobilities above 7 cm ² V ^–1 s ^–1 Liu, Yao; Tolentino, Jason; Gibbs, Markelle Nano Letters, Vol. 13, Issue 4 https://doi.org/10.1021/nl304753n	journal	March 2013
A Solution NMR Toolbox for Characterizing the Surface Chemistry of Colloidal Nanocrystals Hens, Zeger; Martins, José C. Chemistry of Materials, Vol. 25, Issue 8 https://doi.org/10.1021/cm303361s	journal	February 2013
Energy Level Modification in Lead Sulfide Quantum Dot Thin Films through Ligand Exchange Brown, Patrick R.; Kim, Donghun; Lunt, Richard R. ACS Nano, Vol. 8, Issue 6 https://doi.org/10.1021/nn500897c	journal	May 2014
“Darker-than-Black” PbS Quantum Dots: Enhancing Optical Absorption of Colloidal Semiconductor Nanocrystals via Short Conjugated Ligands Giansante, Carlo; Infante, Ivan; Fabiano, Eduardo Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja510739q	journal	January 2015
Colloidal Arenethiolate-Capped PbS Quantum Dots: Optoelectronic Properties, Self-Assembly, and Application in Solution-Cast Photovoltaics Giansante, Carlo; Carbone, Luigi; Giannini, Cinzia The Journal of Physical Chemistry C, Vol. 117, Issue 25 https://doi.org/10.1021/jp403066q	journal	June 2013
Near-Unity Quantum Yields from Chloride Treated CdTe Colloidal Quantum Dots Page, Robert C.; Espinobarro-Velazquez, Daniel; Leontiadou, Marina A. Small, Vol. 11, Issue 13 https://doi.org/10.1002/smll.201402264	journal	October 2014
The coordination chemistry of nanocrystal surfaces Owen, Jonathan Science, Vol. 347, Issue 6222 https://doi.org/10.1126/science.1259924	journal	February 2015

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Nahinfrarotaktive Bleichalkogenid‐Quantenpunkte: Herstellung, postsynthetischer Ligandenaustausch und Anwendungen in Solarzellen Shrestha, Aabhash; Batmunkh, Munkhbayar; Tricoli, Antonio Angewandte Chemie, Vol. 131, Issue 16 https://doi.org/10.1002/ange.201804053	journal	February 2019
Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15257	journal	May 2017
The dynamic surface chemistry of colloidal metal chalcogenide quantum dots Grisorio, Roberto; Quarta, Danila; Fiore, Angela Nanoscale Advances, Vol. 1, Issue 9 https://doi.org/10.1039/c9na00452a	journal	January 2019
Enhancing light absorption by colloidal metal chalcogenide quantum dots via chalcogenol(ate) surface ligands Giansante, Carlo Nanoscale, Vol. 11, Issue 19 https://doi.org/10.1039/c9nr01785b	journal	January 2019
Enhanced photoredox activity of CsPbBr ₃ nanocrystals by quantitative colloidal ligand exchange Lu, Haipeng; Zhu, Xiaolin; Miller, Collin The Journal of Chemical Physics, Vol. 151, Issue 20 https://doi.org/10.1063/1.5129261	journal	November 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
QD surface chemistry
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Title: In situ spectroscopic characterization of a solution-phase X-type ligand exchange at colloidal lead sulphide quantum dot surfaces

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