Enhanced hydrogen production through methane dry reforming: Evaluating the effects of promoter-induced variations in reducibility, basicity, and crystallinity on Ni/ZSM-5 catalyst performance

The pursuit of sustainable hydrogen production through the conversion of methane (CH₄) and carbon dioxide (CO₂), two prevalent greenhouse gases, is advanced by utilizing cost-effective Ni-supported catalysts within the framework of methane dry reforming. Utilizing crystalline porous zeolite, specifically ZSM-5, enhances the dispersion of nickel (Ni) across the catalyst surface and within its pore channels, hence increasing catalytic efficiency. Herein, we investigate the impact of incorporating various promoters (Ce, Cs, Cu, Fe, Sr) into the 5Ni/ZSM-5 catalyst, systematically examining how these modifications influence the reducibility, basicity, and crystallinity of the catalyst’s active sites, thereby affecting its hydrogen yield potential.

Our findings reveal that the inferior activity of Cu-promoted catalysts is due to the depletion of basic sites and larger NiO crystallite size (than rest-promoted catalysts). The introduction of Fe results in a highly dispersed Ni with a stable NiFe phase, but dilution of active sites results in low hydrogen yield. Conversely, Sr promotion enhances the basicity and accessibility of NiO active sites both on the surface and within the pore channels of the zeolite, leading to a notable hydrogen yield of 28 % at 700℃ after 300 min. Furthermore, the addition of 2 wt% ceria significantly optimizes Ni dispersion within the pore channels and surges the maximum population of basic sites (including the presence of very strong basic sites), achieving 35 % hydrogen yield at 700 °C and ∼ 70 % at 800℃. This investigation underscores the critical role of promoter-induced modifications in enhancing catalyst performance for hydrogen production, contributing to the development of more efficient and sustainable energy conversion technologies.