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Microwave heating provides a rapid method for the heterogeneous nucleation of noble metal particles on perovskite support materials for electrocatalytic purposes. To succeed, dielectric tuning of perovskite materials becomes fundamental. Herein, the dielectric engineering of the BaMnO3 perovskite system is carried out through the use of B‐site doping to give BaTi0.5Mn0.5O3. Using a combination of atomic‐scale imaging and electron energy loss spectroscopy (EELS), the preferential filling of the M1 and M3 B‐sites with Mn and Ti ions in the 12R‐rhombohedral perovskite structure is established. While the addition of Ti in the BaMnO3 system has no detrimental effects on the presence of the oxygen reduction reaction (ORR) active Mn3+ states at the surface, it does alter the dielectric constant and loss tangent, thus facilitating the heterogeneous nucleation of Pt nanoparticles on BaTi0.5Mn0.5O3 via rapid microwave heating. Higher Pt loading regimes are found to increase the size and aggregation of the nucleated particles, thus reducing their ORR activity. Therefore, lower Pt loading not only reduces costs but improves overall activity. This work represents future possibilities for the dielectric engineering of perovskite and similar support materials to aid in the quick and easy formation of stable noble metal‐support catalytic systems. [ABSTRACT FROM AUTHOR]

In relation to perovskites, tweaking the oxidation state of the B‐site cation is fundamental to controlling the catalytic activity of these materials, thus necessitating a complete characterization of surface oxidation states. Herein, using a combination of atomic‐scale imaging and spectroscopic techniques, structure‐property correlation in barium manganese oxide (BaMnO3) is established for the oxygen reduction reaction (ORR). Electron energy loss spectroscopy (EELS) on the synthesized BaMnO3 find the rods to contain an amorphous surface layer with reduced Mn3+ states compared to Mn4+ states in the bulk. Consequently, the BaMnO3 rods show electrocatalytic activity for the ORR, which originates from the presence of Mn3+ at the rod surface. Furthermore, heating of the samples in air at 300 and 800 °C results in a decrease in the number of Mn3+ states, and thus lowering of the ORR activity. This study represents a step‐stone study in understanding the mechanism of ORR activity and its association to the Mn3+ state at the perovskite's surface, opening up possibilities for further surface engineering and tuning catalytic properties. [ABSTRACT FROM AUTHOR]

In relation to perovskites, tweaking the oxidation state of the B‐site cation is fundamental to controlling the catalytic activity of these materials, thus necessitating a complete characterization of surface oxidation states. Herein, using a combination of atomic‐scale imaging and spectroscopic techniques, structure‐property correlation in barium manganese oxide (BaMnO3) is established for the oxygen reduction reaction (ORR). Electron energy loss spectroscopy (EELS) on the synthesized BaMnO3 find the rods to contain an amorphous surface layer with reduced Mn3+ states compared to Mn4+ states in the bulk. Consequently, the BaMnO3 rods show electrocatalytic activity for the ORR, which originates from the presence of Mn3+ at the rod surface. Furthermore, heating of the samples in air at 300 and 800 °C results in a decrease in the number of Mn3+ states, and thus lowering of the ORR activity. This study represents a step‐stone study in understanding the mechanism of ORR activity and its association to the Mn3+ state at the perovskite's surface, opening up possibilities for further surface engineering and tuning catalytic properties. [ABSTRACT FROM AUTHOR]

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO 2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO 2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core-shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge-discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li + -ion batteries., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)