Ultrathin-layer chromatography nanostructures modified by atomic layer deposition

• ALD metal oxides (Al2O3, ZrO2, ZnO) coated nanostructured GLAD columnar thin films.
• Composite nanomaterials were characterized using TEM and gas adsorption porosimetry.
• ALD coatings <5 nm thick covered GLAD columns and dictated UTLC analyte retention.
• Combining GLAD and ALD permits independent morphology and surface chemistry control.
• New chromatography stationary phases can be explored with this coupled technique.

Stationary phase morphology and surface chemistry dictate the properties of ultrathin-layer chromatography (UTLC) media and interactions with analytes in sample mixtures. In this paper, we combined two powerful thin film deposition techniques to create composite chromatography nanomaterials. Glancing angle deposition (GLAD) produces high surface area columnar microstructures with aligned macropores well-suited for UTLC. Atomic layer deposition (ALD) enables precise fabrication of conformal, nanometer-scale coatings that can tune surfaces of these UTLC films. We coated ∼5 μm thick GLAD SiO2 UTLC media with <10 nm thick ALD metal oxides (Al2O3, ZrO2, and ZnO) to decouple surface chemistry from the underlying GLAD scaffold microstructure. The effects of ALD coatings on GLAD UTLC media were investigated using transmission electron microscopy (TEM), gas adsorption porosimetry, and lipophilic dye separations. The results collectively show that the most significant changes occur over the first few nanometers of ALD coating. They further demonstrate independent control of film microstructure and surface characteristics. ALD coatings can enhance complex GLAD microstructures to engineer new composite nanomaterials potentially useful in analytical chromatography.