Oxygen adsorption on Au clusters and a rough Au(111) surface: The role of surface flatness, electron confinement, excess electrons, and band gap

It has been shown recently that while bulk gold is chemically inert, small Au clusters are catalytically active. The reasons for this activity and its dramatic dependence on cluster size are not understood. We use density functional theory to study O2 binding to Au clusters and to a Au(111) surface modified by adsorption of Au clusters on it. We find that O2 does not bind to a flat face of a planar Au cluster, even though it binds well to its edge. Moreover, O2 binds to Au clusters deposited on a Au(111) surface, even though it does not bind to Au(111). This indicates that a band gap is not an essential factor in binding O2, but surface roughness is. Adding electrons to the surface of a Au(111) slab, on which one has deposited a Au cluster, increases the binding energy of O2. However, adding electrons to a flat Ausurface has no effect on O2binding energy. These observations have a simple explanation: in clusters and in the rough surface, the highest occupied molecular orbital (HOMO) is localized and its charge density sticks out in the vacuum. This facilitates charge transfer into the π* orbital of O2, which induces the molecule to bind to gold. A flat face of a cluster or a flat bulk surface tends to delocalize the HOMO, diminishing the ability of the surface to bind O2. The same statements are true for the LUMO orbital, which is occupied by the additional electron given to the system to charge the system negatively

Outcome of a workshop

International audience; In tackling agricultural challenges, policy-makers in sub-Saharan Africa (SSA) have increasingly considered genetically modified (GM) crops as a potential tool to increase productivity and to improve product quality. Yet, as elsewhere in the world, the adoption of GM crops in SSA has been marked by controversy, encompassing not only the potential risks to animal and human health, and to the environment, but also other concerns such as ethical issues, public participation in decision-making, socio-economic factors and intellectual property rights. With these non-scientific factors complicating an already controversial situation, disseminating credible information to the public as well as facilitating stakeholder input into decision-making is essential. In SSA, there are various and innovative risk communication approaches and strategies being developed, yet a comprehensive analysis of such data is missing. This gap is addressed by giving an overview of current strategies, identifying similarities and differences between various country and institutional approaches and promoting a way forward, building on a recent workshop with risk communicators working in SSA

Catalytic abatement of trichloroethylene over Mo and/or W-based bronzes

[EN] In this paper we present the results of the synthesis, characterization and catalytic behaviour of Mo(W)¿Nb¿V¿O mixed metal oxides bronzes for the catalytic oxidation of trichloroethylene. The catalysts were prepared hydrothermally with different Mo/W/Nb/V/P atomic ratio and heat-treated at 500 and 700 °C. They were characterized by several techniques as N2-adsorption, X-ray diffraction, FTIR, SEM-EDS, temperature programmed desorption, temperature programmed reduction, UV¿vis, Fourier transformed infrared spectroscopy of adsorbed pyridine and 18O/16O isotope exchange. X-ray diffraction patterns (XRD) of samples heat-treated at 500 °C suggest the presence of a semi-crystalline material with a diffraction peak at ca. 2¿ = 22.2°, while XRD patterns of samples heat-treated at 700 °C show the formation of a tetragonal tungsten bronze (TTB) structure. The activity for the catalytic abatement of trichloroethylene strongly depends on the heat-treatment temperature and the catalyst composition. Thus, samples with W/(Mo + W) atomic ratios of 0.25-0.75 and heat-treated at 500 °C are the most active ones. The enhanced activity has been related to the remarkable higher surface area of the catalyst and to the catalyst composition which influences the acid characteristics as well as the reducibility and reoxidation of the catalysts. The importance of the oxygen dissociation on the catalyst surface and the diffusion of oxygen species through the catalyst are also discussed.The authors wish to thank DGICYT in Spain (Project CTQ2009-14495 and CSD2009-00050-CONSOLIDER/INGENIO 2010) and Universitat Politecnica de Valencia for the financial support. N.B.R. acknowledges Catedra Cemex Sostenibilidad (UPV) for a fellowship. M.D.S. acknowledges Universitat Politecnica de Valencia for a fellowship.Blanch Raga, N.; Soriano Rodríguez, MD.; Palomares Gimeno, AE.; Concepción Heydorn, P.; Martínez Triguero, LJ.; López Nieto, JM. (2013). Catalytic abatement of trichloroethylene over Mo and/or W-based bronzes. Applied Catalysis B: Environmental. 130-131:36-43. https://doi.org/10.1016/j.apcatb.2012.10.016S3643130-13

Solar light photocatalytic CO2 reduction: general considerations and selected bench-mark photocatalysts

[EN] The reduction of carbon dioxide to useful chemicals has received a great deal of attention as an alternative to the depletion of fossil resources without altering the atmospheric CO2 balance. As the chemical reduction of CO2 is energetically uphill due to its remarkable thermodynamic stability, this process requires a significant transfer of energy. Achievements in the fields of photocatalysis during the last decade sparked increased interest in the possibility of using sunlight to reduce CO2. In this review we discuss some general features associated with the photocatalytic reduction of CO2 for the production of solar fuels, with considerations to be taken into account of the photocatalyst design, of the limitations arising from the lack of visible light response of titania, of the use of co-catalysts to overcome this shortcoming, together with several strategies that have been applied to enhance the photocatalytic efficiency of CO2 reduction. The aim is not to provide an exhaustive review of the area, but to present general aspects to be considered, and then to outline which are currently the most efficient photocatalytic systems.Financial support by the Marie Curie project PIEF-GA-2011-298740 and Generalitat Valenciana (Prometeo 20121013) is gratefully acknowledged. J.A.M.-A. acknowledges the assistance of the CSIC for their award of a Postdoctoral JAE-Doc contract.Neatu, S.; Maciá Agulló, JA.; García Gómez, H. (2014). Solar light photocatalytic CO2 reduction: general considerations and selected bench-mark photocatalysts. International Journal of Molecular Sciences. 15(4):5246-5262. https://doi.org/10.3390/ijms15045246S5246526215

A substoichiometric tungsten oxide catalyst provides a sustainable and efficient counter electrode for dye-sensitized solar cells

Development of Pt-free catalyst materials for the counter electrode (CE) in dye-sensitized solar cells (DSSCs) has been regarded as one of the crucial steps to improving energy conversion efficiency and cost effectiveness of DSSCs. In this work, low cost tungsten oxide (WO3-x) counter electrodes, prepared by annealing tungsten metal sheets under an Ar and low O2atmosphere, exhibited high catalytic activity and energy conversion efficiency. The highest efficiency achieved here for DSSCs with WO3-xcounter electrodes, was 5.25%, obtained from a 500 °C annealed tungsten sheet. TEM and XPS analysis suggested the formation of sub-stoichiometric tungsten oxide layer (∼WO2.6) with the presence of W6+, W5+and W4+oxidation states at the tungsten metal surface after the 500 °C annealing. Only W6+and W5+oxidation states were detected after a 600 °C annealing indicating the formation of a more stoichiometric tungsten oxide layer (∼WO2.8) and resulting in a drop in efficiency of the DSSC. We suggest that mixed valence tungsten states account for the excellent catalytic activity and good electrical conductivity as evidenced by the highest cyclic voltammetry response of 0.76 mA/cm2and the lowest impedance value of 44.33 Ω, respectively

Development of scalable and versatile nanomaterial libraries for nanosafety studies: polyvinylpyrrolidone (PVP) capped metal oxide nanoparticles

The potential long-term environmental impact of manufactured nanomaterials (NMs) remains poorly understood, and the need to better predict NM fate and transformations and chronic effects is particularly urgent. Compared to their bulk counterparts, manufactured NMs can have distinct physical and chemical characteristics, which influence their behaviour, stability and toxicity. It is therefore essential to develop standard and reference NM libraries for environmental nanoscience and nano(eco)toxicology, and to facilitate a move towards computational prediction of NM fate, through quantitative structure–activity relationships for example. The aim of this work was to develop and fully characterise one such library, which included comparable NMs with a range of core chemistries, but the same capping agent and size range, for use in future studies to test the hypothesis that the core chemistry is a primary factor in controlling toxicity. The library contained the following NMs: 10k, 40k and 360k PVP capped ceria, zinc oxide and copper oxide (9 NMs in total). The work presented here upholds the underpinning hypothesis that the mechanism of NM formation is the same in all cases, suggesting that the protocol is very robust and has the potential to generate a wide range of comparable metal oxide NMs and potentially expand the library further with doped metal oxide and metal NMs. Characterisation by means of DLS (both size and zeta measurements), UV/Vis, XPS, FT-IR, TEM, STEM, EDX and EELS confirms that the tested synthesis protocol can easily and successfully be used to create stable PVP capped metal oxide NMs of reproducible sizes