Role of Curvature in Stabilizing Boron-Doped Nanocorrugated Graphene.

Boron-doped carbon nanostructures have attracted great interest recently because of their remarkable electrocatalytic performance comparable to or better than that of conventional metal catalysts. In a previous work (Carbon 123, 605 (2017)), we reported that along with significant performance improvement, B doping enhances the oxidation resistance of few-layer graphene (FLG) that provides increased structural stability for intermediate-temperature fuel-cell electrodes. In general, detailed characterization of the atomic and electronic structure transformations that occur in B-doped carbon nanostructures during fuel-cell operation is lacking. In this work, we use aberration-corrected scanning transmission electron microscopy, nanobeam electron diffraction, and electron energy-loss spectroscopy (EELS) to characterize the atomic and electronic structures of B-doped FLG before and after fuel-cell operation. These data point to the nanoscale corrugation of B-doped FLGs as the key factor responsible for increased stability and high corrosion resistance. The similarity of the 1s to π* and σ* transition features in the B K-edge EELS to those in B-doped carbon nanotubes provides an estimate for the curvature of nanocorrugation in B-FLG.

Black Anatase Formation by Annealing of Amorphous Nanoparticles and the Role of the Ti2O3 Shell in Self-Organized Crystallization by Particle Attachment.

We use amorphous titania nanoparticle networks produced by pulsed laser vaporization at room temperature as a model system for understanding the mechanism of formation of black titania. Here, we characterize the transformation of amorphous nanoparticles by annealing in pure Ar at 400 °C, the lowest temperature at which black titania was observed. Atomic resolution electron microscopy methods and electron energy loss spectroscopy show that the onset of crystallization occurs by nucleation of an anatase core that is surrounded by an amorphous Ti2O3 shell. The formation of the metastable anatase core before the thermodynamically stable rutile phase occurs according to the Ostwald phase rule. In the second stage the particle size increases by coalescence of already crystallized particles by a self-organized mechanism of crystallization by particle attachment. We show that the Ti2O3 shell plays a critical role in both black titania transformation and functionality. At 400 °C, Ti2O3 hinders the agglomeration of neighboring particles to maintain a high surface-to-volume ratio that is beneficial for enhanced photocatalytic activity. In agreement with previous results, the thin Ti2O3 surface layer acts as a narrow bandgap semiconductor in concert with surface defects to enhance the photocatalytic activity. Our results demonstrate that crystallization by particle attachment can be a highly effective mechanism for optimizing photocatalytic efficiency by controlling the phase, composition, and particle size distribution in a wide range of self-doped defective TiO2 architectures simply by varying the annealing conditions of amorphous nanoparticles.