Plasma-Catalyst Dynamics: Nonthermal Activation of Strong Metal-Support Interactions.

Nonthermal plasma-surface interactions enable transformative advancements in green chemistry, healthcare, materials processing, pollution abatement, and the ever-growing area of plasma catalysis. In the context of plasma catalysis, the fate of the active sites during plasma treatment has remained enigmatic, and observation of low-temperature plasma-catalyst events has been challenging. The induction of strong metal-support interactions (SMSI) through high-temperature hydrogen treatment is a well-documented and established, yet limited, method to impact selectivity and stability of noble metal catalysts on reducible supports. Thermally driven SMSI occurs through reduction and subsequent migration of the support to the surface of exposed metal sites, thus affecting the catalyst both electronically and geometrically and serving as an ideal system to evaluate dynamic plasma-catalyst interactions. In this study, a dielectric barrier discharge of hydrogen was used to successfully induce a plasma-SMSI state (P-SMSI) in niobia-supported platinum particles at bulk-gas temperatures as low as -30 °C, which enhances the selectivity for propane dehydrogenation and offers conclusive evidence of plasma-catalyst interactions. Time-resolved spectroscopic evidence of this phenomenon was obtained in situ using a cryogenically cooled plasma IR transmission cell, which provided evidence of diffusion-controlled surface migration. Collectively, P-SMSI constitutes a promising, low-impact technology for synthesizing SMSI-enhanced catalysts with controllable active sites, and knowledge of the nonthermal plasma-catalyst dynamics is critical in designing materials for specific applications or selecting conditions of operation.