Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics on Rhodium-Based Catalysts by Operando Raman Spectroscopy

A mechanism for carbon deposition and its impact on the reaction kinetics of Methane Dry Reforming (MDR) using Rhodium-based catalysts is presented. By integrating Raman spectroscopy with kinetic analysis in an operando-annular chemical reactor under strict chemical conditions, we discovered that carbon deposition on a Rh/alpha-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 concentration. The findings elucidate the spatiotemporal development of carbon aggregates on the catalyst surface and their effects on catalytic performance. Furthermore, the proposed mechanism for carbon formation shows that the influence of CO2 on MDR kinetics is an indirect result of carbon accumulation over time frames exceeding the turnover frequency, thus reconciling conflicting reports in the literature regarding CO2 ' s kinetic role in MDR. Kinetic measurements, combined with operando Raman spectroscopy and ex situ microscopy characterization provided new insights on the carbon formation pathway over Rhodium-based catalyst materials during methane dry reforming, which allowed to relate the reaction kinetics with changes in catalyst structure under true reaction conditions. image