Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots
Abstract
We report that cesium lead halide perovskites are an emerging class of quantum dots (QDs) that have shown promise in a variety of applications; however, their properties are highly dependent on their surface chemistry. To this point, the thermodynamics of ligand binding remain unstudied. 1H NMR methods are used to quantify the thermodynamics of ligand exchange on CsPbBr3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr3 QD surface, having individual surface densities of 1.2–1.7 nm–2. 10-Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate (Keq = 1.97) at 25 °C while 10-undecenylphosphonic acid undergoes an irreversible ligand exchange. Undec-10-en-1-amine exergonically exchanges with oleylamine (Keq = 2.52) at 25 °C. Finally, exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr3 QDs without etching the nanocrystal surface; increases in steady-state PL intensities are correlated with more strongly bound conjugate base ligands.
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- Univ. of Southern California, Los Angeles, CA (United States). Loker Hydrocarbon Inst.
- Publication Date:
- Research Org.:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1582645
- Alternate Identifier(s):
- OSTI ID: 1463200
- Grant/Contract Number:
- SC0006812; FG02‐11ER46826
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 36; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CsPbBr3; ligands; NMR spectroscopy; perovskites; quantum dots
Citation Formats
Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots. United States: N. p., 2018.
Web. doi:10.1002/anie.201806916.
Smock, Sara R., Williams, Travis J., & Brutchey, Richard L. Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots. United States. https://doi.org/10.1002/anie.201806916
Smock, Sara R., Williams, Travis J., and Brutchey, Richard L. Thu .
"Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots". United States. https://doi.org/10.1002/anie.201806916. https://www.osti.gov/servlets/purl/1582645.
@article{osti_1582645,
title = {Quantifying the Thermodynamics of Ligand Binding to CsPbBr3 Quantum Dots},
author = {Smock, Sara R. and Williams, Travis J. and Brutchey, Richard L.},
abstractNote = {We report that cesium lead halide perovskites are an emerging class of quantum dots (QDs) that have shown promise in a variety of applications; however, their properties are highly dependent on their surface chemistry. To this point, the thermodynamics of ligand binding remain unstudied. 1H NMR methods are used to quantify the thermodynamics of ligand exchange on CsPbBr3 QDs. Both oleic acid and oleylamine native ligands dynamically interact with the CsPbBr3 QD surface, having individual surface densities of 1.2–1.7 nm–2. 10-Undecenoic acid undergoes an exergonic exchange equilibrium with bound oleate (Keq = 1.97) at 25 °C while 10-undecenylphosphonic acid undergoes an irreversible ligand exchange. Undec-10-en-1-amine exergonically exchanges with oleylamine (Keq = 2.52) at 25 °C. Finally, exchange occurs with carboxylic acids, phosphonic acids, and amines on CsPbBr3 QDs without etching the nanocrystal surface; increases in steady-state PL intensities are correlated with more strongly bound conjugate base ligands.},
doi = {10.1002/anie.201806916},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}
Web of Science
Works referenced in this record:
Quantifying Ligand Exchange Reactions at CdSe Nanocrystal Surfaces
journal, June 2016
- Knauf, Robin R.; Lennox, J. Christian; Dempsey, Jillian L.
- Chemistry of Materials, Vol. 28, Issue 13
Monodisperse Formamidinium Lead Bromide Nanocrystals with Bright and Stable Green Photoluminescence
journal, October 2016
- Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
- Journal of the American Chemical Society, Vol. 138, Issue 43
Utilizing Self-Exchange To Address the Binding of Carboxylic Acid Ligands to CdSe Quantum Dots
journal, July 2010
- Fritzinger, Bernd; Capek, Richard K.; Lambert, Karel
- Journal of the American Chemical Society, Vol. 132, Issue 29
Shape Evolution and Single Particle Luminescence of Organometal Halide Perovskite Nanocrystals
journal, February 2015
- Zhu, Feng; Men, Long; Guo, Yijun
- ACS Nano, Vol. 9, Issue 3
Ultra-bright and highly efficient inorganic based perovskite light-emitting diodes
journal, June 2017
- Zhang, Liuqi; Yang, Xiaolei; Jiang, Qi
- Nature Communications, Vol. 8, Issue 1
Colloidal CsPbX 3 (X = Cl, Br, I) Nanocrystals 2.0: Zwitterionic Capping Ligands for Improved Durability and Stability
journal, February 2018
- Krieg, Franziska; Ochsenbein, Stefan T.; Yakunin, Sergii
- ACS Energy Letters, Vol. 3, Issue 3
On the crystal structure of colloidally prepared CsPbBr 3 quantum dots
journal, January 2016
- Cottingham, Patrick; Brutchey, Richard L.
- Chemical Communications, Vol. 52, Issue 30
Highly stable CsPbBr 3 quantum dots coated with alkyl phosphate for white light-emitting diodes
journal, January 2017
- Xuan, Tongtong; Yang, Xianfeng; Lou, Sunqi
- Nanoscale, Vol. 9, Issue 40
Water resistant CsPbX 3 nanocrystals coated with polyhedral oligomeric silsesquioxane and their use as solid state luminophores in all-perovskite white light-emitting devices
journal, January 2016
- Huang, He; Chen, Bingkun; Wang, Zhenguang
- Chemical Science, Vol. 7, Issue 9
Colloidal CsPbBr 3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots
journal, November 2015
- Swarnkar, Abhishek; Chulliyil, Ramya; Ravi, Vikash Kumar
- Angewandte Chemie International Edition, Vol. 54, Issue 51
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics
journal, October 2016
- Swarnkar, A.; Marshall, A. R.; Sanehira, E. M.
- Science, Vol. 354, Issue 6308
Insight into the Ligand-Mediated Synthesis of Colloidal CsPbBr 3 Perovskite Nanocrystals: The Role of Organic Acid, Base, and Cesium Precursors
journal, July 2016
- Pan, Aizhao; He, Bo; Fan, Xiaoyun
- ACS Nano, Vol. 10, Issue 8
Thermal degradation of luminescence in inorganic perovskite CsPbBr 3 nanocrystals
journal, January 2017
- Yuan, Xi; Hou, Xuemin; Li, Ji
- Physical Chemistry Chemical Physics, Vol. 19, Issue 13
Colloidal CsPbBr 3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots
journal, November 2015
- Swarnkar, Abhishek; Chulliyil, Ramya; Ravi, Vikash Kumar
- Angewandte Chemie, Vol. 127, Issue 51
Highly Dynamic Ligand Binding and Light Absorption Coefficient of Cesium Lead Bromide Perovskite Nanocrystals
journal, January 2016
- De Roo, Jonathan; Ibáñez, Maria; Geiregat, Pieter
- ACS Nano, Vol. 10, Issue 2
Surface Chemistry of All Inorganic Halide Perovskite Nanocrystals: Passivation Mechanism and Stability
journal, March 2018
- Yang, Dandan; Li, Xiaoming; Zeng, Haibo
- Advanced Materials Interfaces, Vol. 5, Issue 8
Enhanced mobility CsPbI 3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells
journal, October 2017
- Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.
- Science Advances, Vol. 3, Issue 10
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015
- Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
- Nano Letters, Vol. 15, Issue 6
Works referencing / citing this record:
Halogen Vacancies Enable Ligand‐Assisted Self‐Assembly of Perovskite Quantum Dots into Nanowires
journal, September 2019
- Pan, Jun; Li, Xiyan; Gong, Xiwen
- Angewandte Chemie, Vol. 131, Issue 45
Halogen Vacancies Enable Ligand‐Assisted Self‐Assembly of Perovskite Quantum Dots into Nanowires
journal, November 2019
- Pan, Jun; Li, Xiyan; Gong, Xiwen
- Angewandte Chemie International Edition, Vol. 58, Issue 45
Synergistic Surface Passivation of CH 3 NH 3 PbBr 3 Perovskite Quantum Dots with Phosphonic Acid and (3‐Aminopropyl)triethoxysilane
journal, March 2019
- Xu, Ke; Vickers, Evan T.; Rao, Longshi
- Chemistry – A European Journal, Vol. 25, Issue 19
Unveiling the Photo‐ and Thermal‐Stability of Cesium Lead Halide Perovskite Nanocrystals
journal, October 2019
- Boote, Brett W.; Andaraarachchi, Himashi P.; Rosales, Bryan A.
- ChemPhysChem, Vol. 20, Issue 20
Exploring the surface chemistry of cesium lead halide perovskite nanocrystals
journal, January 2019
- Grisorio, Roberto; Di Clemente, Milvia Elena; Fanizza, Elisabetta
- Nanoscale, Vol. 11, Issue 3
Self-assembly of a robust hydrogen-bonded octylphosphonate network on cesium lead bromide perovskite nanocrystals for light-emitting diodes
journal, January 2019
- Brown, Alasdair A. M.; Hooper, Thomas J. N.; Veldhuis, Sjoerd A.
- Nanoscale, Vol. 11, Issue 25
Insights into the role of the lead/surfactant ratio in the formation and passivation of cesium lead bromide perovskite nanocrystals
journal, January 2020
- Grisorio, Roberto; Fanizza, Elisabetta; Allegretta, Ignazio
- Nanoscale, Vol. 12, Issue 2
Surface coordination chemistry of germanium nanocrystals synthesized by microwave-assisted reduction in oleylamine
journal, January 2020
- Smock, Sara R.; Tabatabaei, Katayoon; Williams, Travis J.
- Nanoscale, Vol. 12, Issue 4
Ultra-stable CsPbBr 3 nanocrystals with near-unity photoluminescence quantum yield via postsynthetic surface engineering
journal, January 2019
- Zu, Yanqing; Dai, Jinfei; Li, Lu
- Journal of Materials Chemistry A, Vol. 7, Issue 45
Effects of interfacial ligand type on hybrid P3HT:CdSe quantum dot solar cell device parameters
journal, August 2019
- Greaney, Matthew J.; Joy, Jimmy; Combs, Blair A.
- The Journal of Chemical Physics, Vol. 151, Issue 7
Resurfacing halide perovskite nanocrystals
journal, May 2019
- Almeida, Guilherme; Infante, Ivan; Manna, Liberato
- Science, Vol. 364, Issue 6443
An overview on enhancing the stability of lead halide perovskite quantum dots and their applications in phosphor-converted LEDs
journal, January 2019
- Wei, Yi; Cheng, Ziyong; Lin, Jun
- Chemical Society Reviews, Vol. 48, Issue 1
Facile purification of CsPbX 3 (X = Cl−, Br−, I−) perovskite nanocrystals
journal, September 2019
- Wang, Chujie; Chesman, Anthony S. R.; Yin, Wenping
- The Journal of Chemical Physics, Vol. 151, Issue 12