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Probing NO2 Reactivity on Coinage Metal Surfaces through Liquid Crystal Orientational Responses.

Evangelos Smith1, Huaizhe Yu2, Hanyu Zhang2

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Liquid crystals on metal surfaces offer a new optical method for detecting nitrogen dioxide (NO2) at low concentrations. Their orientation changes reveal NO2 interactions and surface chemistry, aiding environmental monitoring.

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Area of Science:

  • Surface Science
  • Materials Science
  • Environmental Science

Background:

  • Understanding nitrogen oxides (NOx) reactivity at interfaces is crucial for environmental monitoring and air quality control.
  • Liquid crystals (LCs) offer potential as optical probes for interfacial phenomena.

Purpose of the Study:

  • To investigate the use of 5CB liquid crystals on coinage metal surfaces (Au, Ag, Cu) as an optical probe for NO2 adsorption and interfacial interactions.
  • To elucidate the substrate-dependent NO2 reactivity and speciation on metal surfaces influenced by LC overlayers.

Main Methods:

  • Preparation of Au, Ag/Au, and Cu/Au surfaces using electron-beam and electrochemical deposition.
  • Characterization using X-ray photoelectron spectroscopy (XPS) to determine surface oxides.
  • Analysis of LC orientation changes via polarized light microscopy and PM-IRRAS upon NO2 exposure.
  • Theoretical investigation using Density Functional Theory (DFT) calculations.

Main Results:

  • 5CB liquid crystals exhibited substrate-dependent orientations (planar on Au/Cu, perpendicular on Ag/Au).
  • NO2 exposure induced reversible planar-to-perpendicular transitions on Au and irreversible transitions on Cu/Au, linked to surface oxidation.
  • 5CB on Ag/Au showed no response to NO2, with DFT indicating altered NO2 speciation due to LC presence.
  • Substrate composition and oxidation state critically govern NO2 adsorption and speciation.

Conclusions:

  • 5CB LCs on coinage metals provide a sensitive optical method for detecting NO2 at ppm levels.
  • The study highlights the significant role of substrate surface chemistry and oxidation state in interfacial NO2 reactions.
  • LCs can modify surface reaction pathways and NO2 speciation on metal surfaces.