Metal–Organic\nFramework-Templated Synthesis\nof Nickel–Alumina Nanocatalysts Improves Catalyst–Support\nInteraction for Higher Activity and Stability in Biogas Reforming\nunder Controlled Oxidizing Conditions

Tri-reforming methane with CO<sub>2</sub>, O<sub>2</sub>, and H<sub>2</sub>O mixtures requires a delicate\nbalance of dry-reforming,\npartial\noxidation, and steam-reforming reactions to improve the CO<sub>2</sub> conversion and H<sub>2</sub>/CO ratio. Nickel–alumina has\nbeen reported before for the tri-reforming of methane, although at\nhigher temperatures (>900 °C). This is because the current\napproaches\nfor nickel–alumina synthesis are ineffective in generating\nstronger catalyst–support interactions necessary to maintain\nhigher active sites and stall carbon nanotube (CNT) deposition. Here,\nwe report a synthesis method that allows controlled loading of nickel\non alumina-based MIL-53 metal–organic framework followed by\ncalcination to generate 2.5–10 wt % nickel nanoparticles dispersed\non alumina. The 5 wt % nickel–alumina mixtures resulted in\nnanometer-sized crystallites, better metal dispersion, and more active\nsites for enhanced catalytic activity. This optimal loading of nickel\nallows stronger interaction with alumina for over 100 h of stable\nperformance of tri-reforming at 800 °C, achieving ∼98%\nCH<sub>4</sub> conversion, ∼36% CO<sub>2</sub> conversion,\nand no carbon deposition while producing Fischer–Tropsch-ready\nfeed containing a H<sub>2</sub>/CO ratio of 3.2.