The Role of Plasma-Emitted Photons in Plasma-Catalytic CO2 Splitting over TiO2 Nanotube-Based Electrodes

The plasma-catalytic conversion of CO2 is a promising route toward sustainable fuel and chemical production under mild operating conditions. However, many aspects still need to be better understood to improve performance and better understand the catalyst-plasma synergies. Among them, one aspect concerns understanding whether photons emitted by plasma discharges could induce changes in the catalyst, thereby promoting interaction between plasma species and the catalyst. This question was addressed by investigating the CO2 splitting reaction in a planar dielectric barrier discharge (pDBD) reactor using titania-based catalysts that simultaneously act as discharge electrodes. Four systems were examined feeding pure CO2 at different flow rates and applied voltage: bare titanium gauze, anodically formed TiO2 nanotubes (TiNT), TiNT decorated with Ag–Au nanoparticles (TiNTAgAu), and TiNT supporting Ag–Au nanoparticles coated with polyaniline (TiNTAgAu/PANI). The TiNTAgAu exhibited the highest CO2 conversion (35% at 10 mL min−1 and 5.45 kV) and the most intense optical emission, even in the absence of external light irradiation, suggesting that the improvement is primarily attributed to plasma–nanoparticle interactions and self-induced localized surface plasmon resonance (si-LSPR) rather than conventional photocatalytic pathways. SEM analyses indicated severe plasma-induced degradation of TiNT and TiNTAgAu surfaces, leading to performance decay over time. In contrast, the TiNTAgAu/PANI catalyst retained structural integrity, with the polymeric coating mitigating plasma etching while maintaining competitive efficiency. There is thus a complex behavior with catalytic performance governed by nanostructure stability, plasmonic enhancement, and the interfacial protection. The results demonstrate how integrating plasmonic nanoparticles and conductive polymers can enable the rational design of durable and efficient plasma-photocatalysts for CO2 valorization and other plasma-assisted catalytic processes.