Synthesis, structure and magnetic properties ofβ-MnO2nanorods

We present synthesis, structure and magnetic properties of structurally well-ordered single-crystalline β-MnO2nanorods of 50–100 nm diameter and several µm length. Thorough structural characterization shows that the basic β-MnO2material is covered by a thin surface layer (∼2.5 nm) of α-Mn2O3phase with a reduced Mn valence that adds its own magnetic signal to the total magnetization of the β-MnO2nanorods. The relatively complicated temperature-dependent magnetism of the nanorods can be explained in terms of a superposition of bulk magnetic properties of spatially segregated β-MnO2and α-Mn2O3constituent phases and the soft ferromagnetism of the thin interface layer between these two phases

Environmental controls, morphodynamic processes, and ecogeomorphic interactions of barchan to parabolic dune transformations

The transformation of barchans into parabolic dunes has been observed in various dune systems around the world. Precise details of how environmental controls influence the dune transformation and stabilisation mechanism, however, remain poorly understood. A ‘horns-anchoring’ mechanism and a ‘nebkhas-initiation’ mechanism have previously been proposed and selected environmental controls on the transformation have been explored by some modelling efforts, but the morphodynamic processes and eco-geomorphic interactions involved are unclear and comparison between different dune systems is challenging. This study extends a cellular automaton model, informed by empirical data from fieldwork and remote sensing, to fully explore how vegetation characteristics, boundary conditions, and wind regime influence the transformation process and the resulting dune morphologies. A ‘dynamic growth function’ is introduced for clump-like perennials to differentiate between growing and non-growing seasons and to simulate the development of young plants into mature plants over multiple years. Modelling results show that environmental parameters interact with each other in a complex manner to impact the transformation process. The study finds a fundamental power-law relation between a non-dimensional parameter group, so-called the ‘dune stabilising index’ (S⁎), and the normalised migration distance of the transforming dune, which can be used to reconstruct paleo-environmental conditions and monitor the impacts of changes in climate or land-use on a dune system. Four basic eco-geomorphic interaction zones are identified which bear different functionality in the barchan to parabolic dune transformation. The roles of different environmental controls in changing the eco-geomorphic interaction zones, transforming processes, and resulting dune morphologies are also clarified

In Search of Excellence: Convex versus Concave Noble Metal Nanostructures for Electrocatalytic Applications

Controlling the shape of noble metal nanoparticles is a challenging but important task in electrocatalysis. Apart from hollow and nanocage structures, concave noble metal nanoparticles are considered a new class of unconventional electrocatalysts that exhibit superior electrocatalytic properties as compared with those of conventional nanoparticles (including convex and flat ones). Herein, several facile and highly reproducible routes for synthesizing nanostructured concave noble metal materials reported in the literature are discussed, together with their advantages over noble metal nanoparticles with convex shapes. In addition, possible ways of optimizing the synthesis procedure and enhancing the electrocatalytic characteristics of concave metal nanoparticles are suggested. Nanostructured noble metals with concave features are found to show better catalytic activity and stability hence improve their practical applicability in electrocatalysis

Tuning the Valence of the Cerium Center in (Na) Phthalocyaninato and Porphyrinato Cerium Double-Deckers by Changing the Nature of the Tetrapyrrole Ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles