Doping Pd2+ into NinCeOx nanofibers promotes low-temperature CO2 methanation

Abstract

CO2 methanation at low temperatures is still a challenge. Herein, NinCeOx (n = 1–3) and Ni2.5Pd0.1CeOx nanofibers by electrospinning is reported. The main advantage of this method is to obtain the highly dispersed precursor of palladium, nickel, and cerium, overcoming the difficulty of uniform mixing in conventional preparation methods. The Ni2.5Pd0.1CeOx nanofiber catalyst exhibited outstanding catalytic performance at low temperatures (CO2 conversion rate = 90.4 %, CH4 selectivity = 99.6 % at 230 °C) along with exceptional stability over 300 h. EPR, Raman, and O 1s XPS confirmed that Pd2+ doping increased oxygen vacancy concentration. In-situ infrared spectroscopy indicated that CO2 methanation on Ni2.5CeOx and Ni2.5Pd0.1CeOx catalysts followed the formate pathways. Pd2+ doping increased the number of surface oxygen vacancies and hydroxyl groups, thus increasing the amount of bicarbonates and formates. DFT calculations suggested that Pd2+ doping increased CO2 adsorption energy, and confirmed surface hydroxyl groups and bicarbonate being beneficial for CO2 methanation, consequently enhancing the activity of Ni2.5Pd0.1CeOx catalyst especially at low temperatures.