Oxygen-Terminated (1 × 1) Reconstruction of Reduced Magnetite Fe 3 O 4 (111).

The (111) facet of magnetite (Fe 3 O 4 ) has been studied extensively by experimental and theoretical methods, but controversy remains regarding the structure of its low-energy surface terminations. Using density functional theory (DFT) computations, we demonstrate three reconstructions that are more favorable than the accepted Fe oct2 termination under reducing conditions. All three structures change the coordination of iron in the kagome Fe oct1 layer to be tetrahedral. With atomically resolved microscopy techniques, we show that the termination that coexists with the Fe tet1 termination consists of tetrahedral iron capped by 3-fold coordinated oxygen atoms. This structure explains the inert nature of the reduced patches.