Tailoring manganese oxide with atomic precision to increase surface site availability for oxygen reduction catalysis.

Controlling the structure of catalysts at the atomic level provides an opportunity to establish detailed understanding of the catalytic form-to-function and realize new, non-equilibrium catalytic structures. Here, advanced thin-film deposition is used to control the atomic structure of La2/3Sr1/3MnO3, a well-known catalyst for the oxygen reduction reaction. The surface and sub-surface is customized, whereas the overall composition and d-electron configuration of the oxide is kept constant. Although the addition of SrMnO3 benefits the oxygen reduction reaction via electronic structure and conductivity improvements, SrMnO3 can react with ambient air to reduce the surface site availability. Placing SrMnO3 in the sub-surface underneath a LaMnO3 overlayer allows the catalyst to maintain the surface site availability while benefiting from improved electronic effects. The results show the promise of advanced thin-film deposition for realizing atomically precise catalysts, in which the surface and sub-surface structure and stoichiometry are tailored for functionality, over controlling only bulk compositions.

Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB.

The 'MAlB' phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, mostly amorphous, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36-0.49 µΩm) and - like a metal - drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm(-1)K(-1) at 26 °C). In the 25-1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10(-6 )K(-1). Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures.