Ligand exchange is
a critical step for tuning the properties of
quantum dots (QDs), as well as functionalization for wide applications.
Previous studies have categorized X-, L-, and Z-types of ligands and
classified the ligand exchange process accordingly. Many works have
investigated the influences of ligand exchange on the optical properties
of QDs. To date, however, the thermodynamic implications of ligand
exchange are not well understood, and the mechanisms of distinct effects
of the ligands of the same type are unclear. To address these issues,
ligand exchange reactions of the oleate-capped CdSe QDs with alkylamines
of different carbon chain length, namely, n-butylamine
(C4Am), n-octylamine (C8Am), n-dodecylamine (C12Am), were investigated using 1H nuclear magnetic resonance (1H NMR) spectroscopy,
fluorescence spectroscopy, X-ray photoelectron spectroscopy (XPS),
Fourier transform infrared spectroscopy (FTIR), etc. 1H
NMR studies showed that the equilibrium constants (K
eq) for the desorption of the Z-type ligand (cadmium oleate)
from the surface of CdSe QDs, as promoted by the L-type ligands (alkylamines),
were in the order of C4Am > C8Am > C12Am, presumably highlighting the small steric barrier of ligands
with
short carbon chain. In addition, the ligand exchange was studied by
fluorescence titration at varied temperatures from a perspective of
ligand adsorption following the desorption of cadmium oleate. The
binding constants were of magnitude 103 M–1. A “two-step ligand exchange” (TSLE) model was developed
to describe the ligand desorption–adsorption process with thermodynamic
perspectives. The increased length of the carbon chain brought not
only increasing steric barrier but also increasing van der Waals interactions,
exhibiting a double-edged sword effect in ligand exchange. The ligand
exchange with C8Am contributed the most negative value
of ΔH and ΔS since the
van der Waals interactions between C8Am and neighboring
ligands were stronger than that for C4Am, whereas its steric
barrier was weaker than that of C12Am. These demonstrated
the importance of ligand–ligand interactions, relatively less
documented in the previous studies, besides the predominance of the
nanocrystal–ligand interactions. UV–vis absorption spectroscopic
and fluorescence lifetime studies further showed that the ligand exchange
with all three alkylamines affected optical properties of CdSe QDs
to some extent. Powder X-ray diffraction (XRD) and transmission electron
microscopy (TEM) results showed that the ligand exchange process basically
did not affect the crystal structure and core size of the CdSe QDs.
Our work had proposed a conceivable mechanism for ligand exchange,
elucidated the thermodynamic implications, and provided a reasonable
guidance for selection of suitable ligands.