Effects of Capping Agents on the Oxygen Reduction Reaction Activity and Shape Stability of Pt Nanocubes

We investigated the formation of Pt nanocubes (NCs) and their electrocatalytic oxygen reduction reaction (ORR) properties and structural stability using two different capping agents, namely, polyvinylpyrrolidone (PVP) and oleylamine (OAm). The mono-dispersity of the obtained Pt NCs and their interactions with PVP and OAm were analyzed by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier-transformed infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The TEM data show a high mono-dispersity (82 %) and a large mean particle size (9-10 nm) for the Pt NCs obtained by the oleylamine-assisted method compared to those prepared via the PVP-assisted procedure (68 %, 6–7 nm). FTIR, XPS, and TGA data show that PVP and OAm still remain at the Pt surface, despite washing. Interestingly, the OAm-capped Pt NCs show significantly higher electrochemically active surface area (ECSA) and ORR activity than the PVP-capped ones. An accelerated stress protocol, however, reveals that the OAm-capped NCs possess a poor structural stability during electrochemical cycling. The loss of a defined surface arrangement in the NCs is connected with a transformation into a near-spherical particle shape. In contrast, the PVP-capped NCs mainly retain their particle shape due to their strong capping behavior. In addition, we have developed a degradation model for NCs as a function of electrochemical parameters such as upper potential and cycle number. Altogether, we provide fundamental insights into the electronic interactions between capping agent and Pt NCs and the role of the adsorption strength of the capping agent in improving the electrochemical ORR performance as well as the structural stability of shape-controlled nanoparticles.     

Sustainable Co‐Synthesis of Glycolic Acid,Formamides and Formates from 1,3‐Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites

Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3‐dihyroxyacetone (DHA) using a cheap supported Cu/Al₂O₃ catalyst with single active Cu^II species. By combining EPR spin‐trapping and operando ATR‐IR experiments, different mechanisms for the co‐synthesis of GA, formates, and formamides have been derived, in which ^.OH radicals formed from H₂O₂ by a Fenton‐like reaction play a key role.     

Preparing a journey to the east of 208Pb with ISOLTRAP: Isobaric purification at A = 209 and new masses for 211-213Fr and 211Ra

With the Penning trap mass spectrometer ISOLTRAP, located at ISOLDE/CERN, preparatory work has been performed towards mass and decay studies on neutron-rich Hg and Tl isotopes beyond N = 126 . The properties of these isotopes are not well known because of large isobaric contamination coming mainly from surface-ionised Fr. Within the studies, production tests using several target-ion source combinations were performed. It was furthermore demonstrated around mass number A = 209 that the resolving power required to purify Fr is achievable with ISOLTRAP. In addition, masses of several isobaric contaminants, ^211-213Fr and ²¹¹Ra , were determined with a three-fold improved precision. The results influence masses of more than 20 other nuclides in the ²⁰⁸Pb region.     

FE2-Simulations in Elasto-Plasticity using Statistically Similar Representative Volume Elements

In the field of direct homogenization methods large representative volume elements (RVE's) cause a high computational cost, which is indicated by a large number of history variables allocating a large amount of memory. Additionally, a high computation time is necessary to solve the systems of equations on the micro-scale as well as on the macro-scale. In this contribution we focus on random microstructures consisting of a continuous matrix phase with a high number of embedded inclusions with arbitrary morphology. We present a method for the construction of statistically similar representative volume elements (SSRVE's) which are characterized by a much less complexity than usual RVE's in order to obtain an efficient simulation tool. The basic goal of the underlying procedure is to find a SSRVE, where some selected statistical measures describing the inclusion morphology are as close as possible to the ones of the original arbitrary microstructure. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of boron carbide after applying shear deformations under a pressure to 55 GPa

Transmission electron microscopy has been used to study the structural features of boron carbide treated in a high-pressure shear chamber with diamond anvils in the pressure range 25–55 GPa. Such a treatment has been shown to lead to the predominant crack formation along planes {10 11 } and {10 12} and also the formation of polytypes in the {10 11} planes and strain bands in the {10 12} planes.     

Effects of Al(OH)O nanoparticle agglomerate size in epoxy resin on tension,bending, and fracture properties

Several epoxy Al(OH)O (boehmite) dispersions in an epoxy resin are produced in a kneader to study the mechanistic correlation between the nanoparticle size and mechanical properties of the prepared nanocomposites. The agglomerate size is set by a targeted variation in solid content and temperature during dispersion, resulting in a different level of stress intensity and thus a different final agglomerate size during the process. The suspension viscosity was used for the estimation of stress energy in laminar shear flow. Agglomerate size measurements are executed via dynamic light scattering to ensure the quality of the produced dispersions. Furthermore, various nanocomposite samples are prepared for three-point bending, tension, and fracture toughness tests. The screening of the size effect is executed with at least seven samples per agglomerate size and test method. The variation of solid content is found to be a reliable method to adjust the agglomerate size between 138–354 nm during dispersion. The size effect on the Young’s modulus and the critical stress intensity is only marginal. Nevertheless, there is a statistically relevant trend showing a linear increase with a decrease in agglomerate size. In contrast, the size effect is more dominant to the sample’s strain and stress at failure. Unlike microscaled agglomerates or particles, which lead to embrittlement of the composite material, nanoscaled agglomerates or particles cause the composite elongation to be nearly of the same level as the base material. The observed effect is valid for agglomerate sizes between 138–354 nm and a particle mass fraction of 10 wt%.     

Strong Convergence in Stabilised Degenerate Convex Problems

Solutions to non–convex variational problems typically exhibit enforced finer and finer oscillations called microstructures such that the infimal energy is not attained. Those oscillations are physically meaningful, but finite element approximations typically experience dramatic difficulty in their reproduction. The relaxation of the non–convex minimisation problem by (semi–)convexification leads to a macroscopic model for the effective energy. The resulting discrete macroscopic problem is degenerate in the sense that it is convex but not strictly convex. This paper discusses a modified discretisation by adding a stabilisation term to the discrete energy. It will be announced that, for a wide class of problems, this stabilisation technique leads to strong H¹–convergence of the macroscipic variables even on unstructured triangulations. This is in contrast to the work [2] for quasi–uniform triangulations and enables the use of adaptive algorithms for the stabilised formulations. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bifurcation analysis of a stochastic non-smooth friction model

Non-smooth friction systems such as systems with dry friction show several bifurcation phenomena. The discontinuity of these so called slip-stick vibrations makes these systems interesting and there has been a lot of research in this field, see for example Hinrichs [1]. Due to the non-smooth friction force even the deterministic system shows a rich bifurcation behavior. Measurements indicate that the friction coefficient which plays a large role in the system behavior is not deterministic but can be described as a friction characteristic with added white noise. Therefore, the stochastic characteristic is introduced into the non-smooth system and the change of the bifurcation behavior is studied. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gradient induced motion control of drifting solitary structures in a nonlinear optical single feedback experiment

We realize an absolute position control of drifting dissipative optical solitons by injecting an incoherent amplitude parameter gradient onto the nonlinear optical system. This allows for two-dimensional, arbitrary control patterns. The control of the soliton drift velocity is studied applying a periodic, hexagonally shaped modulation. The guiding of dissipative solitons by one- and two-dimensional parameter modulations is demonstrated. Furthermore, one-dimensional, line-shaped parameter modulations are designed to act as barriers for dissipative solitons, allowing implementations of position selectors for solitons. The interaction of dissipative optical solitons with barriers is studied for different barrier parameters.