posted on 2020-07-06, 15:04authored byStefan
M. Piontek, Mark DelloStritto, Bijoya Mandal, Tim Marshall, Michael L. Klein, Eric Borguet
Unlike metal or semiconductor
electrodes, the surface charge resulting
from the protonation or deprotonation of insulating mineral oxides
is highly localized and heterogeneous in nature. In this work the
Stark active CN stretch of potassium thiocyanate is used as
a molecular probe of the heterogeneity of the interfacial electrostatic
potential at the α-Al2O3(0001)/H2O interface. Vibrational sum frequency generation (vSFG) measurements
performed in the OH stretching region suggest that thiocyanate species
organize interfacial water similarly to halide ions. Changes in the
electrostatic potential are then tracked via Stark shifts of the vibrational
frequency of the thiocyanate stretch. Our vSFG measurements show that
we can simultaneously measure the vSFG response of SCN– ions experiencing charged and neutral surface sites. We assign local
potentials of +308 and −154 mV to positively and negatively
charged aluminol groups that are present at pH = 4 and pH = 10, respectively.
Thiocyanate anions at positively charged surface sites and negatively
charged surface sites and those participating in contact ion pairing
adopt similar orientations and are oppositely oriented relative to
thiocyanate ions near neutral surface sites. All four species followed
Langmuir adsorption isotherms. Density functional theory–molecular
dynamics (DFT-MD) simulations of SCN– near the neutral
α-Al2O3(0001)/H2O interface
show that the vSFG response in the CN stretch region originates
from a SCN–H–O–Al complex, suggesting the surface
site specificity of these experiments. To our knowledge this is the
first spectroscopic measurement of local potentials associated with
a heterogeneously charged surface. The ability to probe the evolution
of local charges in situ could provide vital insight into many industrial,
electrochemical, and geochemically relevant interfaces.