Plasma-assisted catalysis is the process of electrically activating gases in the plasma-phase at low temperatures and ambient pressure to drive reactions on catalyst surfaces. Plasma-assisted catalytic processes combine conventional heterogeneous surface reactions, homogeneous plasma phase reactions, and coupling between plasma-generated species and the catalyst surface. Herein, we perform kinetically controlled ammonia synthesis measurements in a dielectric barrier discharge (DBD) plasma-assisted catalytic reactor. We decouple contributions due to plasma phase reactions from the overall plasma-assisted catalytic kinetics by performing plasma-only experiments. By varying the gas composition, temperature, and discharge power, we probe how macroscopic reaction conditions affect plasma-assisted ammonia synthesis on three different gamma-alumina-supported transition metal catalysts (Ru, Co, and Ni). Our experiments indicate that the overall reaction and plasma-phase reaction are first-order in both N-2 and H-2. In contrast, the rate contributions due to plasma-catalyst interactions are first-order in N-2 but zeroth order in H-2. Furthermore, we find that the tuning of the plasma discharge power is more effective in controlling catalytic performance than the increasing of bulk gas temperature in plasma-assisted ammonia synthesis. Finally, we show that adding a catalyst to the DBD reaction alters the way that productivity scales with the specific energy input (SEI).
