Transition-Metal Oxides/Carbides@Carbon Nanotube Composites as Multifunctional Electrocatalysts for Challenging Oxidations and Reductions

The rapid development of renewable-energy technologies such as water splitting, rechargeable metal–air batteries, and fuel cells requires highly efficient electrocatalysts capable of the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER). Herein, we report a facile sonication-driven synthesis to deposit the molecular manganese vanadium oxide precursor [Mn₄V₄O₁₇(OAc)₃]³⁻ on multiwalled carbon nanotubes (MWCNTs). Thermal conversion of this composite at 900 °C gives nanostructured manganese vanadium oxides/carbides, which are stably linked to the MWCNTs. The resulting composites show excellent electrochemical reactivity for ORR and OER, and significant reactivity enhancements compared with the precursors and a Pt/C reference are reported. Notably, even under harsh acidic conditions, long-term OER activity at low overpotential is reported. In addition, we report exceptional activity of the composites for the industrially important Cl₂ evolution from an aqueous HCl electrolyte. The new composite material shows how molecular deposition routes leading to highly active and stable multifunctional electrocatalysts can be developed. The facile design could in principle be extended to multiple catalyst classes by tuning of the molecular metal oxide precursor employed.     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

Light emission from nanocrystalline silicon clusters embedded in silicon dioxide: Role of the suboxide states

Silicon clusters embedded in a silicon dioxide matrix were prepared by ultrasound-assisted implantation resulting in a modified concentration of suboxide states as revealed by high-resolution photoelectron spectroscopy. It is suggested that ultrasound treatment results in formation of different interface structure between silicon cluster and silicon dioxide matrix which is characterized by a distinctly reduced concentration of the suboxide states. It is observed that photoluminescence properties are strongly correlated with the concentration of the suboxide states thereby providing an evidence that besides a quantum confinement effect a closer look at the chemical composition of the nc-Si/SiO₂ system is important.     

Systematic optimisation of high-performance liquid chromatographic separation by varying the temperature, gradient, and stationary phase

Optimisation of the separation of a synthetic drug mixture by HPLC is performed by changing both continuous variables, i.e. mobile phase composition and temperature, and categorical variables, here the stationary phase. The retention of solutes is described on the basis of a general linear model in which the different columns are modelled by indicator variables. From the solute-specific retention models the global separation optimum is evaluated on the basis of multidimensional window diagrams using relative retentions of all peak pairs as the figure-of-merit.     

Nano-electrospray ionization mass spectrometry: addressing analytical problems beyond routine

The advent of nano-electrospray ionization (nano-ESI) has considerably extended the usability of ESI in the analytical mass spectrometric laboratory. One of the remarkable features of nano-ESI is its extremely low sample consumption. Only a few microliters of analyte solution (10(-5)-10(-8) M) are sufficient for molecular weight determination and structural investigations by MS/MS. But nano-ESI is more than just a minimized-flow ESI; the low solvent flow rate also affects the mechanism of ion formation. As a consequence, the area of ESI-MS applications is significantly enhanced. Oligosaccharides, glycosides as well as glycoproteins can be analyzed more easily than with normal ion spray. The same holds for the analysis of non-covalent complexes sprayed directly from aqueous solutions.     

The influence of a γ-oxygen in the spacer of liquid crystal side group polysiloxanes on their ferroelectric properties

Two types of side group polysiloxanes which differ in their spacer between backbone and mesogenic part were synthesized via polymer analogous reaction. The impact of an oxygen atom localized in the γ position to the siloxane main chain on the ferroelectric properties was investigated. In addition, the link between the terminal chiral moiety and the mesogenic part in each series was varied. The phase transition behaviour, spontaneous polarization and the electro-optical response time for the two series of polymers are compared. The mesophase structures were determined by X-ray measurements on magnetically oriented samples at different temperatures. The additional oxygen atom in the spacer near to the main chain leads to broader range smectic C* phases and shorter electro-optical response times, which suggests that the ether linkage promotes a better decoupling between main chain and mesogenic side group.