Unravelling the Influence of Nd 3+ and Pm 3+ Dopants on the Electronic Structure and Methane Activation Over CeO 2 (111) Surfaces

Abstract A comprehensive quantum chemical investigation has been performed to tune the catalytic properties of bare and Nd/Pm‐doped CeO 2 (111) for methane (CH 4 ) activation. Dopants strengthen adsorption of CH 4 leading to comparatively longer desorption time at 298 K. Improved charge transfer in the case of modified CeO 2 (111) surface shows the reduction of bandgap from 2.15 eV to 0.92 (Nd‐doped) and 1.19 eV (Pm‐doped) CeO 2 , a necessary factor for understanding their catalytic properties. DOS analysis exhibits an additional energy level in Nd/Pm‐doped CeO 2 (111), suggesting an easier charge transfer. Similarly, PDOS analysis reveals a stronger interaction between CH 4 and CeO 2 surface. Higher activation barriers have been noticed for pristine CeO 2 at O11 (1.85 eV), O14 (1.59 eV), and O2 (2.73 eV). However, dopants significantly reduces the activation barrier, enhancing their catalytic activity for CH 4 activation. These findings may help to design and develop efficient materials for methane activation.