Plasma-Catalytic CO(2) Hydrogenation over a Pd/ZnO Catalyst: In Situ Probing of Gas-Phase and Surface Reactions

[Image: see text] Plasma-catalytic CO(2) hydrogenation is a complex chemical process combining plasma-assisted gas-phase and surface reactions. Herein, we investigated CO(2) hydrogenation over Pd/ZnO and ZnO in a tubular dielectric barrier discharge (DBD) reactor at ambient pressure. Compared to the CO(2) hydrogenation using Plasma Only or Plasma + ZnO, placing Pd/ZnO in the DBD almost doubled the conversion of CO(2) (36.7%) and CO yield (35.5%). The reaction pathways in the plasma-enhanced catalytic hydrogenation of CO(2) were investigated by in situ Fourier transform infrared (FTIR) spectroscopy using a novel integrated in situ DBD/FTIR gas cell reactor, combined with online mass spectrometry (MS) analysis, kinetic analysis, and emission spectroscopic measurements. In plasma CO(2) hydrogenation over Pd/ZnO, the hydrogenation of adsorbed surface CO(2) on Pd/ZnO is the dominant reaction route for the enhanced CO(2) conversion, which can be ascribed to the generation of a ZnO(x) overlay as a result of the strong metal–support interactions (SMSI) at the Pd–ZnO interface and the presence of abundant H species at the surface of Pd/ZnO; however, this important surface reaction can be limited in the Plasma + ZnO system due to a lack of active H species present on the ZnO surface and the absence of the SMSI. Instead, CO(2) splitting to CO, both in the plasma gas phase and on the surface of ZnO, is believed to make an important contribution to the conversion of CO(2) in the Plasma + ZnO system.