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

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

Journal Article · Sun Nov 06 23:00:00 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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1334589

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

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

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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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
Exchange equilibria of carboxylate-terminated ligands at PbS nanocrystal surfaces Kessler, Melody L.; Starr, Hannah E.; Knauf, Robin R. Physical Chemistry Chemical Physics, Vol. 20, Issue 36 https://doi.org/10.1039/c8cp04275f	journal	January 2018
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
PbS QDs
QD surface chemistry
ligand exchange

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

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