Surface phase diagrams of pristine and hydroxylated barium hexaferrite surfaces from first-principles atomistic thermodynamics

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Barium hexaferrite (BHF) is a ferrimagnet, whose hexagonal unit cell presents five iron crystallographic sites along the c-axis. At the nanoscale, BHF nanoparticles grow in the form of platelets, characterized by a low thickness along its principal magnetization axis (c-axis), displaying uniaxial magnetic anisotropy with the easy axis pointing perpendicular to the platelet. This unique property of BHF nanoplatelets has lead to a variety of novel applications, which often require surface functionalization. However, it has been observed that the nanoplatelets display two different surface morphologies depending on the stage/conditions of preparation. To ground these experimental observations, we employ the ab initio thermodynamics framework to perform a systematic investigation of the thermodynamic stability of BHF bulk terminations under a wide range of chemical conditions. We calculate the surface phase diagrams of pristine and hydroxylated bulk terminations along the c-axis. For pristine terminations, two different iron terminated surfaces are preferred: the barium containing 2b termination (Ba-rich conditions) and the 4f2 iron terminated surface (Ba-poor conditions). In the presence of water, the hydroxylated oxygen-terminated surfaces (12k-O) are identified as the most stable ones at Ba-poor conditions and low pH values, whereas the hydroxylated 2b surface is preferred at high pH and Ba-rich conditions.