Harvesting Lost Photons: Plasmon and Upconversion Enhanced Broadband Photocatalytic Activity in Core@Shell Microspheres Based on Lanthanide‐Doped NaYF4, TiO2, and Au

Efficiently harvesting solar energy for photocatalysis remains very challenging. Rational design of architectures by combining nanocomponents of radically different properties, for example, plasmonic, upconversion, and photocatalytic properties, offers a promising route to improve solar energy utilization. Herein, the synthesis of novel, plasmonic Au nanoparticle decorated NaYF₄:Yb³⁺, Er³⁺, Tm³⁺‐core@porous‐TiO₂‐shell microspheres is reported. They exhibit high surface area, good stability, broadband absorption from ultraviolet to near infrared, and excellent photocatalytic activity, significantly better than the benchmark P25 TiO₂. The enhanced activity is attributed to synergistic effects from nanocomponents arranged into the nanostructured architecture in such a way that favors the efficient charge/energy transfer among nanocomponents and largely reduced charge recombination. Optical and energy‐transfer properties are modeled theoretically to support our interpretations of catalytic mechanisms. In addition to yielding novel materials and interesting properties, the current work provides physical insights that can contribute to the future development of plasmon‐enhanced broadband catalysts.     

Tetrazoles: Unique Capping Ligands and Precursors for Nanostructured Materials

Capping agents play an important role in the colloidal synthesis of nanomaterials because they control the nucleation and growth of particles, as well as their chemical and colloidal stability. During recent years tetrazole derivatives have proven to be advanced capping ligands for the stabilization of semiconductor and metal nanoparticles. Tetrazole‐capped nanoparticles can be prepared by solution‐phase or solventless single precursor approaches using metal derivatives of tetrazoles. The solventless thermolysis of metal tetrazolates can produce both individual semiconductor nanocrystals and nanostructured metal monolithic foams displaying low densities and high surface areas. Alternatively, highly porous nanoparticle 3D assemblies are achieved through the controllable aggregation of tetrazole‐capped particles in solutions. This approach allows for the preparation of non‐ordered hybrid structures consisting of different building blocks, such as mixed semiconductor and metal nanoparticle‐based (aero)gels with tunable compositions. Another unique property of tetrazoles is their complete thermal decomposition, forming only gaseous products, which is employed in the fabrication of organic‐free semiconductor films from tetrazole‐capped nanoparticles. After deposition and subsequent thermal treatment these films exhibit significantly improved electrical transport. The synthetic availability and advances in the functionalization of tetrazoles necessitate further design and study of tetrazole‐capped nanoparticles for various applications.     

The organization and control of an evolving interdependent population

Starting with Darwin, biologists have asked how populations evolve from a low fitness state that is evolutionarily stable to a high fitness state that is not. Specifically of interest is the emergence of cooperation and multicellularity where the fitness of individuals often appears in conflict with that of the population. Theories of social evolution and evolutionary game theory have produced a number of fruitful results employing two-state two-body frameworks. In this study, we depart from this tradition and instead consider a multi-player, multi-state evolutionary game, in which the fitness of an agent is determined by its relationship to an arbitrary number of other agents. We show that populations organize themselves in one of four distinct phases of interdependence depending on one parameter, selection strength. Some of these phases involve the formation of specialized large-scale structures. We then describe how the evolution of independence can be manipulated through various external perturbations.     

Energy and environment : Nordic energy scenarios for 2010 and 2030

The concept of a sustainable energy sector has received wide attention since the publication of the Brundtland Report in 1987. This paper analyses the possibilities of establishing by 2010 and 2030 an energy system in the Nordic countries which prevents the critical loads of NO_x and SO₂ respectively on the most vulnerable Nordic ecological systems being exceeded. In addition, the present concentration of CO₂ in the atmosphere should not be significantly exceeded within a time horizon to around 2050. Different scenarios have been investigated in order to analyse the scope for attaining such a sustainable energy development within the limits of existing technologies and known potentials of renewable energy sources. Data on the technologies are available in a special catalogue.     

Dielectric and piezoelectric properties of PbFe1/2Nb1/2O3-PbTiO3 ceramics from the morphotropic phase boundary compositional range

Dielectric, X-ray, and piezoelectric studies of highly-resistive Li-doped (1-x)PbFe(1/2)Nb(1/2)O(3)-(x)PbTiO(3) (PFN-xPT) ceramics from the 0 ≤ x ≤ 0.2 range fabricated by solid-state synthesis and usual sintering have been carried out. Distinct anomalies of dielectric and piezoelectric parameters, corresponding to the transition between rhombohedral (monoclinic) and tetragonal ferroelectric phases, have been observed in pure PFN and PFN-xPT compositions with PbTiO(3) content up to 8 mol.%. The x,T-phase diagram of the PFN-xPT solid solution system has been constructed using these data.     

Redox doping behaviour of poly(3,4-ethylenedithiothiophene) - The counterion effect

Poly(3,4-ethylenedithiothiophene) - PEDTT, an alkylene sulphur derivative of PEDOT, presents itself as an interesting polymer with a number of disparate redox and chromic properties compared to its close analogue - PEDOT. In this study we present the results of an investigation into the electrochemical doping process of PEDTT, using four different electrolyte solutions, differing in anion content of the chosen salt. The results show that the anion identity plays a key role in the redox reactions accompanying these processes in what could be interpreted as anion ionochromism. In situ UV-Vis spectroelectrochemical experiments reveal an intriguing double electrochromic transition of PEDTT films during their oxidative doping, going from golden-yellow through green to pomegranate - a quality not so common within the family of electroactive conjugated polymers. The evolution of each UV-Vis spectrum over a potential range indicates that different redox states of the polymer are responsible for the chromatic changes. In the reduction half-cycle, the dedoping process of PEDTT appears to follow a path dissimilar to the p-doping one, featuring only one, direct electrochromic transition of the film’s colour, bypassing the green state, and a distinct two-step bleaching process of doping-induced charge carrier bands. The observed electrochemical and spectral phenomena have been accredited to the specific redox behaviour of doping-induced radical cation and cationic defect states interacting with the dithioalkylene sulphur atom.