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Ordering Transitions of Liquid Crystals Triggered by Metal Oxide-catalyzed Reactions of Sulfur Oxide Species

Abstract:

Liquid crystals (LCs), when supported on reactive surfaces, undergo changes in ordering that can propagate over distances of micrometers, thus providing a general and facile mechanism to amplify atomic-scale transformations on surfaces into the optical scale. While reactions on organic and metal substrates have been coupled to LC-ordering transitions, metal oxide substrates, which offer unique catalytic activities for reactions involving atmospherically important chemical species such as oxidized sulfur species, have not been explored. Here, we investigate this opportunity by designing LCs that contain 4′-cyanobiphenyl-4-carboxylic acid (CBCA) and respond to surface reactions triggered by parts-per-billion concentrations of SO2gas on anatase (101) substrates. We used electronic structure calculations to pbkp_redict that the carboxylic acid group of CBCA binds strongly to anatase (101) in a perpendicular orientation, a pbkp_rediction that we validated in experiments in which CBCA (0.005 mol %) was doped into an LC (4′-n-pentyl-4-biphenylcarbonitrile). Both experiment and computational modeling further demonstrated that SO3-like species, produced by a surface-catalyzed reaction of SO2with H2O on anatase (101), displace CBCA from the anatase surface, resulting in an orientational transition of the LC. Experiments also reveal the LC response to be highly selective to SO2over other atmospheric chemical species (including H2O, NH3, H2S, and NO2), in agreement with our computational pbkp_redictions for anatase (101) surfaces. Overall, we establish that the catalytic activities of metal oxide surfaces offer the basis of a new class of substrates that trigger LCs to undergo ordering transitions in response to chemical species of relevance to atmospheric chemistry.