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/α-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.

Mechanistic and multiscale aspects of thermo-catalytic CO2 conversion to C1 products.

The increasing environmental concerns due to anthropogenic CO2 emissions have called for an alternate sustainable source to fulfill rising chemical and energy demands and reduce environmental problems. The thermo-catalytic activation and conversion of abundantly available CO2, a thermodynamically stable and kinetically inert molecule, can significantly pave the way to sustainably produce chemicals and fuels and mitigate the additional CO2 load. This can be done through comprehensive knowledge and understanding of catalyst behavior, reaction kinetics, and reactor design. This review aims to catalog and summarize the advances in the experimental and theoretical approaches for CO2 activation and conversion to C1 products via heterogeneous catalytic routes. To this aim, we analyze the current literature works describing experimental analyses (e.g., catalyst characterization and kinetics measurement) as well as computational studies (e.g., microkinetic modeling and first-principles calculations). The catalytic reactions of CO2 activation and conversion reviewed in detail are: (i) reverse water-gas shift (RWGS), (ii) CO2 methanation, (iii) CO2 hydrogenation to methanol, and (iv) dry reforming of methane (DRM). This review is divided into six sections. The first section provides an overview of the energy and environmental problems of our society, in which promising strategies and possible pathways to utilize anthropogenic CO2 are highlighted. In the second section, the discussion follows with the description of materials and mechanisms of the available thermo-catalytic processes for CO2 utilization. In the third section, the process of catalyst deactivation by coking is presented, and possible solutions to the problem are recommended based on experimental and theoretical literature works. In the fourth section, kinetic models are reviewed. In the fifth section, reaction technologies associated with the conversion of CO2 are described, and, finally, in the sixth section, concluding remarks and future directions are provided.