LAUSR

ABSTRACT Nitrogen reduction reactions (NRR) under room conditions remain the challenge for N2 activation on metal-based catalysis materials. Herein, the M-doped CeO2(111) (M = Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) with oxygen vacancies, are systematically investigated by spin-polarized DFT+U calculations. We discuss briefly the situation of OVs on pure and reduced cerium, and we found that (I) doping TMs can promote the formation of oxygen defects, apart from Ti and V-dopant, (II) the O atoms are easier to escape connecting to M atoms than the ones of adjacent atoms connecting to the Ce(III), the value of OVs formation energies decrease as the TMs radius decrease. Also, our computational results show that Cr-doped, Mn-doped, Fe-doped, and Co-doped CeO2(111) adsorbs N2 strongly than the stoichiometric surface and other M-doped CeO2 surfaces with adsorption energies of -0.82, -1.02, -0.83 and -1.05 eV. Through COHP analysis, it is found that the predicted active sites have good catalytic performance.