Photoenhanced Degradation of Sarin at Cu/TiO₂ Composite Aerogels: Roles of Bandgap Excitation and Surface Plasmon Excitation

Abstract

Multifunctional composites that couple high-capacity adsorbents with catalytic nanoparticles (NPs) offer a promising route toward the degradation of organophosphorus pollutants or chemical warfare agents (CWAs). We couple mesoporous TiO₂ aerogels with plasmonic Cu nanoparticles (Cu/TiO₂) and characterize the degradation of the organophosphorus CWA sarin under both dark and illuminated conditions. Cu/TiO₂ aerogels combine high dark degradation rates, which are facilitated by hydrolytically active sites at the Cu||TiO₂ interface, with photoenhanced degradation courtesy of semiconducting TiO₂ and the surface plasmon resonance (SPR) of the Cu nanoparticles. The TiO₂ aerogel provides a high surface area for sarin binding (155 m² g^-1), while the addition of Cu NPs increases the abundance of hydrolytically active OH sites. Degradation is accelerated on TiO₂ and Cu/TiO₂ aerogels with O₂. Under broadband illumination, which excites the TiO₂ bandgap and the Cu SPR, sarin degradation accelerates, and the products are more fully mineralized compared to those of the dark reaction. With O₂ and broadband illumination, oxidation products are observed on the Cu/TiO₂ aerogels as the hydrolysis products subsequently oxidize. In contrast, the photodegradation of sarin on TiO₂ is limited by its slow initial hydrolysis, which limits the subsequent photooxidation. Accelerated hydrolysis occurs on Cu/TiO₂ aerogels under visible illumination (>480 nm) that excites the Cu SPR but not the TiO₂ bandgap, confirming that the Cu SPR excitation contributes to the broadband-driven activity. The high hydrolytic activity of the Cu/TiO₂ aerogels combined with the photoactivity upon TiO₂ bandgap excitation and Cu SPR excitation is a potent combination of hydrolysis and oxidation that enables the substantial chemical degradation of organophorphorus compounds.