Exchange equilibria of carboxylate-terminated ligands at PbS nanocrystal surfaces

Literature Information

Publication Date 2018-09-07
DOI 10.1039/C8CP04275F
Impact Factor 3.676
Authors

Melody L. Kessler, Hannah E. Starr, Robin R. Knauf, Kelley J. Rountree, Jillian L. Dempsey


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Abstract

Ligand exchange reactions are commonly used to alter the surface chemistry of metal chalcogenide quantum dots; however, a lack of quantifiable data for these processes limits the rational functionalization of nanomaterials. Here, we quantify the X-type ligand exchange reaction between carboxylate-terminated ligands on PbS quantum dots via1H NMR spectroscopy. Using spectroscopic handles of both the native and exchange ligand, bound and free forms of each have been quantified as a function of exchange ligand concentration. We find that the equilibrium constants for the reaction between oleate-capped PbS quantum dots and undec-10-enoic acid are 2.23 ± 0.50 and 2.14 ± 0.42 for sets of nanocrystals prepared by two different synthetic methods. X-ray photoelectron, absorbance, and emission spectroscopies indicate that the carboxylate exchange reaction does not alter the lead ion coverage of the nanocrystal surface. The quantitative equilibrium constant determined herein can be used to improve control over partial ligand exchange reactions on PbS nanocrystals.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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