Atomistic structures and stabilities of MgAl2O4 surfaces under processing conditions: A first-principles thermodynamics study

Abstract

Surfaces, in contacting ambient environments, are of particular importance for controlling sintering, thin-film growth, and catalytic activity of oxides. Magnesium aluminate spinel (MgAl2O4), an essential oxide for both functional and structural ceramics, has attracted considerable attentions across diverse scientific fields. Nonetheless, a central challenge in rationally manipulating the properties of MgAl2O4 lies in the atomistic understanding of its surface structures under processing conditions. This study presents comprehensive first-principles calculations of MgAl2O4 (110) and (111) polar surfaces with/without off-stoichiometries. We predict from a thermodynamic model the dependence of surface stabilities on critical processing parameters, namely the oxygen partial pressure (PO2) and temperature (T). The findings indicate that at typical sintering temperatures, the non-stoichiometric (110) surface transits from Al/Mg-rich to O-rich with increasing PO2. In contrast, the non-stoichiometric (111) surface stably terminates in a Mg-rich configuration at low PO2, gradually shifting to Al-rich and then to Mg/O-rich as PO2 increases. The correlation between surface off-stoichiometry and stability is elucidated through electronic structure analysis. The investigation offers fundamental insights into surface structures and physicochemical behavior of MgAl2O4, thereby facilitating the rational processing control of complex oxides for applications in catalysis and electronics.