A Dewetted‐Dealloyed Nanoporous Pt Co‐Catalyst Formed on TiO2 Nanotube Arrays Leads to Strongly Enhanced Photocatalytic H2 Production

Pt nanoparticles are typically decorated as co‐catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co‐catalyst loadings is a key challenge in the field. We explore a dewetting‐dealloying strategy to fabricate on TiO₂ nanotubes nanoporous Pt nanoparticles, aiming at improving the co‐catalyst mass activity for H₂ generation. For this, we sputter first Pt‐Ni bi‐layers of controllable thickness (nm range) on highly ordered TiO₂ nanotube arrays, and then induce dewetting‐alloying of the Pt‐Ni bi‐layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO₂ nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt‐decorated TiO₂ structures show a>6 times higher photocatalytic H₂ generation activity compared to structures modified with a comparable loading of dewetted, non‐porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co‐catalyst, which provides an increased surface‐to‐volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co‐catalyst surface for H₂ evolution.     

Shedding Light Onto the Nature of Iron Decorated Graphene and Graphite Oxide Nanohybrids for CO2 Conversion at Atmospheric Pressure

We report on the design and testing of new graphite and graphene oxide-based extended π-conjugated synthetic scaffolds for applications in sustainable chemistry transformations. Nanoparticle-functionalised carbonaceous catalysts for new Fischer Tropsch and Reverse GasWater Shift (RGWS) transformations were prepared: functional graphene oxides emerged from graphite powders via an adapted Hummer's method and subsequently impregnated with uniform-sized nanoparticles. Then the resulting nanomaterials were imaged by TEM, SEM, EDX, AFM and characterised by IR, XPS and Raman spectroscopies prior to incorporation of Pd(II) promoters and further microscopic and spectroscopic analysis. Newly synthesised 2D and 3D layered nanostructures incorporating carbon-supported iron oxide nanoparticulate pre-catalysts were tested, upon hydrogen reduction in situ, for the conversion of CO₂ to CO as well as for the selective formation of CH₄ and longer chain hydrocarbons. The reduction reaction was also carried out and the catalytic species isolated and fully characterised. The catalytic activity of a graphene oxide-supported iron oxide pre-catalyst converted CO₂ into hydrocarbons at different temperatures (305, 335, 370 and 405 °C), and its activity compared well with that of the analogues supported on graphite oxide, the 3-dimensional material precursor to the graphene oxide. Investigation into the use of graphene oxide as a framework for catalysis showed that it has promising activity with respect to reverse gas water shift (RWGS) reaction of CO₂ to CO, even at the low levels of catalyst used and under the rather mild conditions employed at atmospheric pressure. Whilst the γ-Fe₂O₃ decorated graphene oxide-based pre-catalyst displays fairly constant activity up to 405 °C, it was found by GC-MS analysis to be unstable with respect to decomposition at higher temperatures. The addition of palladium as a promoter increased the activity of the iron functionalised graphite oxide in the RWGS. The activity of graphene oxide supported catalysts was found to be enhanced with respect to that of iron-functionalised graphite oxide with, or without palladium as a promoter, and comparable to that of Fe@carbon nanotube-based systems tested under analogous conditions. These results display a significant step forward for the catalytic activity estimations for the iron functionalised and rapidly processable and scalable graphene oxide. The hereby investigated phenomena are of particular relevance for the understanding of the intimate surface morphologies and the potential role of non-covalent interactions in the iron oxide-graphene oxide networks, which could inform the design of nano-materials with performance in future sustainable catalysis applications.     

The Limited Predictive Power of the Pauling Rules

The Pauling rules have been used for decades to rationalise the crystal structures of ionic compounds. Despite their importance, there has been no statistical assessment of the performances of these five empirical rules so far. Here, we rigorously and automatically test all five Pauling rules for a large data set of around 5000 known oxides. We discuss each Pauling rule separately, stressing their limits and range of application in terms of chemistries and structures. We conclude that only 13 % of the oxides simultaneously satisfy the last four rules, indicating a much lower predictive power than expected.     

Transition-Metal-Free Carbon Isotope Exchange of Phenyl Acetic Acids

A transition-metal-free carbon isotope exchange procedure on phenyl acetic acids is described. Utilizing the universal precursor CO₂, this protocol allows the carbon isotope to be inserted into the carboxylic acid position, with no need of precursor synthesis. This procedure enabled the labeling of 15 pharmaceuticals and was compatible with carbon isotopes [¹⁴C] and [¹³C]. A proof of concept with [¹¹C] was also obtained with low molar activity valuable for distribution studies.     

Effects of supervised Self Organising Maps parameters on classification performance

Self Organising Maps (SOMs) are one of the most powerful learning strategies among neural networks algorithms. SOMs have several adaptable parameters and the selection of appropriate network architectures is required in order to make accurate predictions. The major disadvantage of SOMs is probably due to the network optimisation, since this procedure can be often time-expensive.     

A Magnetically Drivable Nanovehicle for Curcumin with Antioxidant Capacity and MRI Relaxation Properties

Curcumin possesses wide‐ranging anti‐inflammatory and anti‐cancer properties and its biological activity can be linked to its potent antioxidant capacity. Superparamagnetic maghemite (γ‐Fe₂O₃), called surface‐active maghemite nanoparticles (SAMNs) were surface‐modified with curcumin molecules, due to the presence of under‐coordinated Fe^III atoms on the nanoparticle surface. The so‐obtained curcumin‐modified SAMNs (SAMN@curcumin) had a mean size of 13±4 nm. SAMN@curcumin was characterized by transmission and scanning electron microscopy, UV/Vis, FTIR, and Mössbauer spectroscopy, X‐ray powder diffraction, bulk susceptibility (SQUID), and relaxometry measurements (MRI imaging). The high negative contrast proclivity of SAMN@curcumin to act as potential contrast agent in MRI screenings was also tested. Moreover, the redox properties of bound curcumin were probed by electrochemistry. SAMN@curcumin was studied in the presence of different electroactive molecules, namely hydroquinone, NADH and ferrocyanide, to assess its redox behavior. Finally, SAMN@curcumin was electrochemically probed in the presence of hydrogen peroxide, demonstrating the stability and reactivity of bound curcumin.     

Synthesis routes for the growth of complex nanostructures

The interest in research on inorganic colloidal nanoparticles has moved to more complex structures, such as anisotropically shaped particles and branched objects. Recently, schemes for the synthesis of heterostructures have also been presented. In this article we discuss the synthesis conditions for spherical and branched nanoparticles. The influence of parameters as temperature and composition of the mixture of surfactants on the shape of the growing particles is discussed. Also, an overview on different approaches for the formation of heterostructures is presented briefly.     

The influence of model parameters and of the thermomechanical coupling on the behavior of shape memory devices

Shape memory materials (SMM) are receiving increasing attention for their use in applications that exploit their dynamic behavior. A thermomechanical model for devices with pseudoelastic behavior has been proposed in previous works [11] (Bernardini and Pence, 2005) [15] (Bernardini and Rega, 2005). The model takes into account several aspects of SMM behavior by means of seven model parameters.In this paper the effect of each parameter on the non-isothermal rate-dependent behavior of the device is studied, by paying particular attention to the effect of the thermomechanical coupling. Some overall synthetic indicators of the behavior of the shape memory device are defined in terms of the model parameters. By evaluating such indicators, a lot of information about the mechanical, thermal and thermomechanical effects on the device behavior can be gained before computing explicitly the response of the shape memory oscillator.The present work may provide a guide for the proper utilization of the model for the investigation of the dynamic response.