Unraveling the effect of particle size of active metals in Ni/MgO on methane activation and carbon growth mechanism

For dry reforming of methane, the active metal particle size of the catalyst has a significant effect on both the reaction activity and the resistance to carbon deposition. In this study, nickel particles of different sizes (Ni13, Ni25, and Ni37) supported on the MgO(100) slab are used to study the mechanism of CH4 activation and carbon growth based on DFT theoretical calculations. According to the results, the energy of adsorption for reaction intermediates changes depending on the size of the active metal. The adsorption process of CH3, CH2, CH and C on Ni25/MgO has a maximum exothermic value. Furthermore, the energy barriers of CH4 four-step dehydrogenation are lowest on Ni25/MgO during the CH4 activation process. The growth process of carbon deposition on the catalysts is also investigated in this work. The results indicate that the growth of carbon from C5 to C6 is difficult to proceed on Ni13/MgO due to size and active site limitation. Additionally, with an increase in particle size of the active metal, the absolute value of growth energy and average carbon binding energy of Cn increase on both Ni25/MgO and Ni37/MgO. It is proved that smaller particle size presents better resistance to carbon deposition. In the studied size range, Ni25/MgO is demonstrated to have greater catalytic activity and better resistance to carbon deposition.