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Title: Designing Janus Ligand Shells on PbS Quantum Dots using Ligand-Ligand Cooperativity

Abstract

We present a combined experimental and theoretical study of ligand-ligand cooperativity during X-type carboxylate-to-carboxylate ligand exchange reactions on PbS quantum dot surfaces. We find that the ligand dipole moment (varied through changing the substituents on the benzene ring of cinnamic acid derivatives) impacts the ligand-exchange isotherms; in particular, ligands with large electron withdrawing character result in a sharper transition from an oleate-dominated ligand shell to a cinnamate-dominated ligand shell. We developed a two-dimensional lattice model to simulate the ligand-exchange isotherms that accounts for the difference in ligand binding energy as well as ligand-ligand cooperativity. Our model shows that ligands with larger ligand-ligand coupling energy exhibit sharper isotherms indicating an order-disorder phase transition. Finally, we developed an anisotropic Janus ligand shell by taking advantage of the ligand-ligand cooperative ligand exchanges. We monitored the Janus ligand shell using 19F nuclear magnetic resonance, showing that when the ligand-ligand coupling energy falls within the order region of the phase diagram, Janus ligand shells can be constructed.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. Argonne National Laboratory; University of Chicago
  3. University of Chicago
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), NREL Director's Fellowship
OSTI Identifier:
1544532
Report Number(s):
NREL/JA-5900-72996
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; ligand coupling; ligand-QD interactions; PbS quantum dots; QD optical properties; QD surface science

Citation Formats

Bronstein, Noah, Martinez, Marissa, Kroupa, Daniel, Voros, Marton, Lu, Haipeng, Brawand, Nicholas, Nozik, Arthur J, Sellinger, Alan, Galli, Giulia, and Beard, Matthew C. Designing Janus Ligand Shells on PbS Quantum Dots using Ligand-Ligand Cooperativity. United States: N. p., 2019. Web. doi:https://dx.doi.org/10.1021/acsnano.9b00191.
Bronstein, Noah, Martinez, Marissa, Kroupa, Daniel, Voros, Marton, Lu, Haipeng, Brawand, Nicholas, Nozik, Arthur J, Sellinger, Alan, Galli, Giulia, & Beard, Matthew C. Designing Janus Ligand Shells on PbS Quantum Dots using Ligand-Ligand Cooperativity. United States. doi:https://dx.doi.org/10.1021/acsnano.9b00191.
Bronstein, Noah, Martinez, Marissa, Kroupa, Daniel, Voros, Marton, Lu, Haipeng, Brawand, Nicholas, Nozik, Arthur J, Sellinger, Alan, Galli, Giulia, and Beard, Matthew C. Mon . "Designing Janus Ligand Shells on PbS Quantum Dots using Ligand-Ligand Cooperativity". United States. doi:https://dx.doi.org/10.1021/acsnano.9b00191.
@article{osti_1544532,
title = {Designing Janus Ligand Shells on PbS Quantum Dots using Ligand-Ligand Cooperativity},
author = {Bronstein, Noah and Martinez, Marissa and Kroupa, Daniel and Voros, Marton and Lu, Haipeng and Brawand, Nicholas and Nozik, Arthur J and Sellinger, Alan and Galli, Giulia and Beard, Matthew C},
abstractNote = {We present a combined experimental and theoretical study of ligand-ligand cooperativity during X-type carboxylate-to-carboxylate ligand exchange reactions on PbS quantum dot surfaces. We find that the ligand dipole moment (varied through changing the substituents on the benzene ring of cinnamic acid derivatives) impacts the ligand-exchange isotherms; in particular, ligands with large electron withdrawing character result in a sharper transition from an oleate-dominated ligand shell to a cinnamate-dominated ligand shell. We developed a two-dimensional lattice model to simulate the ligand-exchange isotherms that accounts for the difference in ligand binding energy as well as ligand-ligand cooperativity. Our model shows that ligands with larger ligand-ligand coupling energy exhibit sharper isotherms indicating an order-disorder phase transition. Finally, we developed an anisotropic Janus ligand shell by taking advantage of the ligand-ligand cooperative ligand exchanges. We monitored the Janus ligand shell using 19F nuclear magnetic resonance, showing that when the ligand-ligand coupling energy falls within the order region of the phase diagram, Janus ligand shells can be constructed.},
doi = {https://dx.doi.org/10.1021/acsnano.9b00191},
journal = {ACS Nano},
number = 4,
volume = 13,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 11, 2020
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