Methane Dry Reforming by Ni–Cu Nanoalloys Anchored on Periclase-Phase MgAlO_<i>x</i> Nanosheets for Enhanced Syngas Production

Abstract

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_<i>x</i> nanosheets were successfully synthesized by a hydrothermal method. These highly dispersed small Ni-Cu alloys strongly interacted with the periclase-phase MgAlO_<i>x</i> 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_cat h for more than 70 h. The hydrogen production rate was maintained at 1.8 mmol/min, and the ratio of H₂/CO was kept at approximately 0.96 under a CH₄ and CO₂ 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_<i>x</i> 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 O₂-TPO results confirmed the significant decrease in carbon deposition on the Ni-Cu alloy catalysts.