Catalytic NH3 oxidation affected by the nanometric roughness of the platinum overlayer.

Pulsed cathodic arc-plasma deposition was employed to create a few nanometre-thick Pt overlayer on a 50 µm-thick Fe-Cr-Al metal (SUS) foil, resulting in an effective NH3 oxidation catalyst fabrication. This catalyst exhibited a turnover frequency (TOF) exceeding 100 times that of Pt nanoparticles. In this study, Pt overlayer catalysts with varying degrees of surface roughness were fabricated using different metal foil substrates: mirror-polished (Pt/p-SUS), unpolished (Pt/SUS) and roughened by the formation of a surface oxide layer (Pt/Al2O3/SUS). The nanoscale roughness was comprehensively analysed using electron microscopy, laser scanning confocal microscopy and chemisorption techniques. NH3 oxidation activity, measured at 200 °C, followed an increasing trend in the order of Pt/Al2O3/SUS < Pt/SUS < Pt/p-SUS, despite a decrease in the apparent Pt surface area in the same order. Consequently, the calculated TOF was markedly higher for Pt/p-SUS (267 min-1) compared to Pt/SUS (107 min-1) and Pt/Al2O3/SUS (≤22 min-1). The smooth Pt overlayer surface also favoured N2 yield over N2O at this temperature. This discovery enhances our fundamental understanding of high-TOF NH3 oxidation over Pt overlayer catalysts, which holds significance for the advancement and industrial implementation of selective NH3 oxidation processes.

Nanometric Iridium Overlayer Catalysts for High-Turnover NH3 Oxidation with Suppressed N2O Formation.

In the present study, we prepared a 12 nm thick Ir overlayer via pulsed cathodic arc plasma deposition on a 50 µm thick Fe-Cr-Al metal (SUS) foil. Using this thin-film catalyst made NH3-O2 reactions more environmentally benign due to a much lower selectivity for undesirable N2O (<5%) than that of a Pt overlayer (∼70%) at 225 °C. Despite its small surface area, Ir/SUS exhibited promising activity as an ammonia slip catalyst according to a turnover frequency (TOF) >70-fold greater than that observed with conventional Ir nanoparticle catalysts supported on γ-Al2O3. We found that the high-TOF NH3 oxidation was associated with the stability of the metallic Ir surface against oxidation by excess O2 present in simulated diesel exhaust. Additionally, we found that the Ir overlayer structure was thermally unstable at reaction temperatures ≥400 °C and at which point the Ir surface coverage dropped significantly; however, thermal deterioration was substantially mitigated by inserting a 250 nm thick Zr buffer layer between the Ir overlayer and the SUS foil substrate (Ir/Zr/SUS). Although N2O formation was suppressed by NH3 oxidation over Ir/Zr/SUS, other undesired byproducts (i.e., NO and NO2) were readily converted to N2 by coupling with a V2O5-WO3/TiO2 catalyst in a second reactor for selective catalytic reduction by NH3. These results demonstrated that this tandem reactor configuration converted NH3 to N2 with nearly complete selectivity at a range of 200-600 °C in the presence of excess O2 (8%) and H2O (10%).