Cetyltrimethylammonium bromide (CTAB) is a widely used surfactant that aids the aqueous synthesis of colloidal
nanoparticles. However, the presence of residual CTAB on nanoparticle
surfaces can significantly impact nanoparticle applications, such
as catalysis and sensing, under hydrated conditions. As such, consideration
of the presence and quantity of CTAB on nanoparticle surfaces under
hydrated conditions is of significance. Herein, as part of an integrated
material characterization framework, we demonstrate the feasibility
of in situ atomic force microscopy (AFM) to detect CTAB on the surface
of Au nanocubes (Au NCs) under hydrated conditions, which enabled
superior characterization compared to conventional spectroscopic methods.
In situ force–distance (FD) spectroscopy and Kelvin probe force
microscopy (KPFM) measurements support additional characterization
of adsorbed CTAB, while correlative in situ AFM and scanning electron
microscopy (SEM) measurements were used to evaluate sequential steps
of CTAB removal from Au NCs across hydrated and dehydrated environments,
respectively. Notably, a substantial quantity of CTAB remained on
the Au NC surface after methanol washing, which was detected in AFM
measurements but was not detected in infrared spectroscopy measurements.
Subsequent electrochemical cleaning was found to be critically important
to remove CTAB from the Au NC surface. Correlative measurements were
also performed on individual nanoparticles, which further validate
the method described here as a powerful tool to determine the extent
and degree of CTAB removal from nanoparticle surfaces. This AFM-based
method is broadly applicable to characterize the presence and removal
of ligands from nanomaterial surfaces under hydrated conditions.