Methane Dry Reforming by Ni-Cu Nanoalloys Anchored on Periclase-Phase MgAlO Nanosheets for Enhanced Syngas Production.

Stable and efficient syngas production via methane dry reforming is highly desirable as it utilizes two greenhouse gases simultaneously. In this work, active Ni-Cu nanoalloys stably anchored on periclase-phase MgAlO nanosheets were successfully synthesized by a hydrothermal method. These highly dispersed small Ni-Cu alloys strongly interacted with the periclase-phase MgAlO nanosheets, on which abundant base sites were accessible. On the optimal catalyst (6Ni6CuMgAl-S), methane and carbon dioxide conversion always reached 85 and 90% at 700 °C under a gas hour speed velocity of 40,000 mL/g h for more than 70 h. The hydrogen production rate was maintained at 1.8 mmol/min, and the ratio of H/CO was kept at approximately 0.96 under a CH and CO flow rate of 25 mL/min. Coke deposition and Ni sintering were effectively suppressed by the formation of a Ni-Cu alloy, the laminar structure, and the periclase phase of the MgAlO support. Moreover, the alloy nanoparticles were reconstructed into a segregated Ni-Cu alloy structure in response to the reaction environment, and this structure was more stable and still active. Density functional theory calculations showed that carbon adsorption was inhibited on the segregated Ni-Cu alloy. Furthermore, the experimental thermogravimetric and O-TPO results confirmed the significant decrease in carbon deposition on the Ni-Cu alloy catalysts.