Computational Catalyst Design for Dry Reforming of Methane: A Review

Because of the recent global warming environmental issues, dry reforming of methane (DRM)─which converts greenhouse gases (CO2 and CH4) into syngases (CO and H2)─is receiving significant attention. Recently, density functional theory (DFT) calculations have been effectively used to obtain fundamental information on DRM reactions. The DFT calculations can provide valuable theoretical knowledge in various heterogeneous catalyst systems, which is difficult to derive from experiments alone due to the complexity of reaction pathways. This work introduces theoretical studies concerning the most plausible reaction pathways, catalytic activities, and stabilities of Ni- and non-Ni-based metal catalysts. The review includes fundamental analyses of reaction mechanisms, catalytic activities, and several strategies to improve the catalytic properties of Ni- and non-Ni-based catalysts. Such strategies include doping, introducing promoters, forming bimetallics, and utilizing various catalyst supports. In addition, DFT-based descriptors provide guidelines for DRM catalyst design in terms of activity and stability. In conclusion, this review also suggests DFT-based analyses of catalysts based on morphological and compositional engineering, such as core–shell nanoparticles, single-atom catalysts, phosphides, and reduced solid solution catalysts. Finally, this review suggests a rational catalyst design for DRM by tuning catalytic properties based on engineered catalyst characteristics under a comprehensive understanding provided by DFT calculations and experiments.