Probing surface-adsorbate interactions through active particle dynamics

Abstract

Adsorbate molecules present in a reaction mixture may bind to and block catalytic sites. Measurement of the surface coverage of these molecules via adsorption isotherms is critical for modeling and design of catalytic reactions on surfaces. However, it is challenging to measure isotherms in solution in a way that is directly relevant to catalytic activity under reaction conditions, particularly since adsorbates may bind with an enormous range of surface affinity parameters. Here we used the motion of self-propelled catalytic Janus particles, which employ the decomposition of hydrogen peroxide fuel as a propulsion mechanism, to determine the effective surface coverage of thioglycerol, furfural, and ethanol on a platinum surface as a function of concentration in aqueous solution by measuring the decrease in active motion due to the blocking of active sites. For strongly adsorbing thioglycerol, this effective coverage was compared and contrasted to the total adsorbed amount measured using inductively-coupled plasma analysis. Demonstrating the broad applicability of this approach, the surface affinity of the three adsorbates spanned more than four orders of magnitude. For each species, the adsorbate-mediated attenuation of active motion occurred over a wide concentration range and was well-described by a Langmuir isotherm. The strongly interacting thioglycerol had the highest affinity towards the surface (K_a = 15.5 ± 4.3 mM^-1) and fully deactivated the active particle motion at surface saturation. Furfural had an intermediate affinity (K_a = 0.42 ± 0.07 mM^-1) but did not fully block H₂O₂ access to the surface at apparent saturation, consistent with a maximum fractional surface coverage of θ_max = 0.67. Ethanol exhibited even lower affinity (K_a = 0.0025 ± 2x10^-4 mM^-1) and its coverage saturated at only θ_max = 0.38. Analysis of isotherms at elevated temperatures enabled direct extraction of the enthalpies of adsorption. The degree of surface coverage at adsorbate saturation appeared to correlate with the relative energies of adsorption for the different adsorbate species and was consistent with adsorbate saturation of one of multiple active site populations towards H₂O₂ decomposition. Moreover, computational investigations into solvent effects on furfural adsorption showed good quantitative agreement with the experimental results. This work leverages unique properties of active particles to explore fundamental catalysis questions and demonstrates a novel paradigm for significant and experimentally accessible multidisciplinary research.

Keywords: Active particles; Adsorption; Catalysis; Surface coverage.