Artificial photosynthesis: from molecular catalysts for light-driven water splitting to photoelectrochemical cells

Photosynthesis has been for many years a fascinating source of inspiration for the development of model systems able to achieve efficient light-to-chemical energetic transduction. This field of research, called "artificial photosynthesis," is currently the subject of intense interest, driven by the aim of converting solar energy into the carbon-free fuel hydrogen through the light-driven water splitting. In this review, we highlight the recent achievements on light-driven water oxidation and hydrogen production by molecular catalysts and we shed light on the perspectives in terms of implementation into water splitting technological devices.     

On the stability of AdS black strings

We explore via linearized perturbation theory the Gregory–Laflamme instability of the black string solutions of Einstein's equations with negative cosmological constant recently discussed in literature. Our results indicate that the black strings whose conformal infinity is the product of time and Sd−3×S¹$S^{d-3}\times S^1$ are stable for large enough values of the event horizon radius. All topological black strings are also classically stable. We argue that this provides an explicit realization of the Gubser–Mitra conjecture.     

3He(e,e′pp) and 3He(e,e′pn) reactions at AmPS and MAMI

This paper reports on measurements of the ³He(e,e′pp) reaction measured at AmPS and the ³He(e,e′pn) reaction measured at MAMI. The measurements were performed in similar kinematics to allow a comparison to be made between the cross sections of the two reactions. Results are shown for both reactions together with a comparison for the ³He(e,e′pp) data with continuum Faddeev calculations.     

Influence of europium ions on structure and crystallization properties of bismuth borate glasses and glass ceramics

Glasses of the xEu₂O₃ · (100?x)[2Bi₂O₃ · B₂O₃] system with 0 ? x ? 25 mol% have been characterized by X-ray diffraction and FTIR spectroscopy measurements. Melting at 1100 °C and the rapid cooling at room temperature permitted us to obtain glass samples. In order to improve the local order and to develop crystalline phases, the glass samples were kept at 625 °C for 24 h. After heat treatment two crystalline phases were put into evidence. One of the crystalline phases was observed for the host glass matrix, the x = 0 mol% sample, and belongs to the cubic system. The second one was observed for the x = 25 mol% sample and was find to be orthorhombic with two unit cell parameters very close to each other. For the samples with 0 < x < 25 mol% there is a mixture of the two mentioned phases. FTIR spectroscopy data suggest that both Bi₂O₃ and B₂O₃ play the glass network former role while the europium ions play the network modifier role in the studied glasses.     

Analysis of the hydrogen bonding in (2-hydroxypropyl)cellulose-poly(acrylic acid) composites by Raman spectroscopy

Novel anisotropic polymer composites obtained by the photopolymerisation of acrylic acid (AA) in lyotropic solutions of (2-hydroxypropyl)cellulose (HPC) were investigated. Raman spectroscopy was used in the study of hydrogen bonding formed by carboxylic groups of poly(acrylic acid) (pAA) between themselves and with the hydroxyl groups of HPC macromolecules. These investigations show that the supramolecular structure of pAA obtained by photopolymerisation contains mainly inner oligomeric forms and cyclic dimer forms, as a consequence of the “matrix polymerisation” of AA. The presence of HPC affects the process of the photopolymerisation of AA, by a redistribution of hydrogen bonding within the system, leading to a different supramolecular structure of pAA. With increasing amounts of HPC the inner oligomeric forms characteristic of bulk pAA disappear. In the composites, the pAA chains probably form the terminal oligomeric structure, with some free COOH groups, as well as hydrogen bonds with HPC.     

Hierarchical Constraint-Based Singularity Avoidance for Multi-Axis Robots

A generalized reflexive approach for Hierarchical Constraint-Based Singularity Avoidance (HCB-SA) is proposed and demonstrated for the multi-axis robot control of a six Degrees Of Freedom (DOF) hybrid manipulator system. The concept utilizes a dynamic adaptation of virtual constraints by introducing virtual damped actuation on the velocity control level and an anisotropic reflexive trajectory deflection depending on the robot constraints on the position control level. Redundant or low priority DOFs can be used to minimize the pose error in the more important DOFs reflexively without calculating new trajectories. Accordingly, the end-effector can be safely controlled in the vicinity of singularities and all constraints in the task and joint space can be surely hold. Furthermore, the proposed cascaded feedback control with the generalized HCB-SA algorithm is able to react on the presence of external disturbances which is validated using software-in-the-loop simulation on the real-time control system. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)