Persistence of acetonitrile bilayers at the interface of acetonitrile/water mixtures with silica.
Previous experiments and simulations have shown that acetonitrile organizes into a lipid-like bilayer at the liquid/silica interface. Recent simulations have further suggested that this bilayer structure persists in mixtures of acetonitrile with water, even at low acetonitrile concentrations. This behavior is indicative of microscopic phase separation of these liquids near silica interfaces and may have important ramifications for the use of acetonitrile in chromatography and heterogeneous catalysis. To explore this phenomenon, we have used vibrational sum-frequency-generation spectroscopy to probe acetonitrile/water mixtures at a silica interface. Our spectra provide evidence that acetonitrile partitions to the hydrated silica interface even when the mole fraction of acetonitrile is as low as 10%. A blue shift is observed in the spectrum of the methyl symmetric stretch upon increasing water mole fraction, in agreement with vibrational spectra of bulk mixtures. Line shape analysis suggests that acetonitrile may exist in the form of bilayer patches at high water mole fractions.
Department of Chemistry & Biochemistry, ‡Institute for Physical Science & Technology, §Maryland NanoCenter, ∥Center for Nanophysics and Advanced Materials, ⊥Chemical Physics Program, University of Maryland , College Park, Maryland 20742, United States.
Christopher A
CA
Rivera
John S
JS
Bender
Katherine
K
Manfred
John T
JT
Fourkas