A synthesis procedure for fabrication of hollow TiO2 spheres of mixed anatase/rutile composition loaded with noble metal nanoparticles (Au, Pt, Pd) is proposed. The materials demonstrated to be functioning photocatalysts for water oxidation. In particular nanoparticles loaded with Pd and Pt showed good catalytic activity in comparison to commercial TiO2 P25.

An experimental setup and routine is presented for evaluating potential catalysts for water splitting by means of measuring Faradaic efficiency in real time by coupled potentiometry and mass spectrometry. The aim was to simulate a potential industrial scale setup and generate results such as H2 production versus power input at a certain potential or current density in addition to electrochemical parameters. Three types of electrodes were tested: A) planar metal electrodes; B) metal foam based electrodes; C) porous electrodes with carbon additive. The results verify that the experimental routine yield desired accuracy, sensitivity and a negligible accumulation of gaseous products in the cell; thus the Faradaic efficiency is measured in real time. The metal based electrodes of category A and B proved to be durable with low overpotentials and high gas output to power input, whereas three tested metal oxide electrodes in C revealed (i) potential-dependent deviation in Faradaic efficiency, (ii) phase decomposition and (iii) an optimum operational power range.

Two electrodes for anodic water oxidation made by direct synthesis of inorganic catalysts onto conductive carbon fibre sheets are evaluated. As catalysts two Co- and Sb-containing phases were tested, that is, Co3Sb4O6F6 and the new compound CoSbO4. The compounds express large differences in their morphology: CoSbO4 grows as thin needles whereas Co3Sb4O6F6 grows as larger facetted crystals. Despite the smaller surface area the latter compound shows a better catalytic performance. When the compound Co3Sb4O6F6 was used it gave a low increase of +0.028 mV h(-1) at an overpotential of eta = 472 mV after 10 h and a stability of +0.48 mV h(-1) at an overpotential of eta = 488 mV after 60 h. The leakages of Co and Sb were negligible and only <0.001 at% Co and approximately 0.02 at% Sb were detected in the electrolyte.

To assess the relatedness and amount of genetic variation of wild and captive Mountain Bongo Tragelaphus eurycerus ssp. isaaci, both non-invasive and invasive samples were efficiently analyzed using SNP's. Mountain Bongo is estimated to remain in Kenyan forest with less than 96 individuals, possibly as low as 73 individuals, split in five subpopulations whereof four populations are isolated from each other. The genetic diversity of wild animals was studied using fecal samples, and using tissue samples from the 62 animals presently held captive at the Mount Kenya Wildlife Conservancy. In strategic conservation of the wild Mountain Bongo, the captive animals constitute a potential genetic input to wild populations. Our study shows there is still genetic variation in the wild population and that the subpopulations are to some extent genetically differentiated. This leads to an overall effective population size of around 14 in the wild population, which is good relative to the small population, but dangerously small for long-term, or even short-term, survival. Most individuals in the wild population were unrelated, while in the captive population most individuals were related at the level of half-sibs. The captive population still host genetic variation and is differentiated slightly to the wild population. Careful restocking from the captive populations could be an effective means to enhance the genetic variation in the wild, but most importantly make the dwindling population less vulnerable to stochastic events.

A sustainable solution for meeting the energy demands at our planet is by utilizing wind-, solar-, wave-, thermal-, biomass- and hydroelectric power. These renewable and CO₂ emission-free energy sources are highly variable in terms of spatial and temporal availability over the Earth, introducing the need for an appropriate method of storing and carrying energy. Hydrogen has gained significant attention as an energy storage- and carrier media because of the high energy density that is exploited within the ‘power-to-gas’ process chain. A robust way of producing sustainable hydrogen is via electrochemical water splitting.

In this work the search for new heterogeneous catalyst materials with the aim of increasing energy efficiency in water splitting has involved methods of both electrochemical water splitting and chemical water oxidation. Some 21 compounds including metal- oxides, oxofluorides, oxochlorides, hydroxide and metals have been evaluated as catalysts. Two of these were synthesized directly onto conductive backbones by hydrothermal methods. Dedicated electrochemical cells were constructed for appropriate analysis of reactions, with one cell simulating an upscale unit accounting for realistic large scale applications; in this cell gaseous products are quantified by use of mass spectrometry. Parameters such as real time faradaic efficiency, production of H₂ and O₂ in relation to power input or overpotentials, Tafel slopes, exchange current density and electrochemical active surface area as well as turnover numbers and turnover frequencies have been evaluated.

Solubility, possible side reactions, the role of the oxidation state of catalytically active elements and the nature of the outermost active surface layer of the catalyst are discussed. It was concluded that metal oxides are less efficient than metal based catalysts, both in terms of energy efficiency and in terms of electrode preparation methods intended for long time operation. The most efficient material was Ni-Fe hydroxide electrodeposited onto Ni metal foam as conductive backbone. Among the other catalysts, Co₃Sb₄O₆F₆ was of particular interest because the compound incorporate a metalloid (Sb) and redox inert F and yet show pronounced catalytic performance.

In addition, performance of materials in water splitting catalysis has been discussed on the basis of results from electron microscopy, solubility experiments and X-ray diffraction data.

The recently described solid solution ( Co,Ni,Mn)(3)Sb4O6F6 has proved stable and efficient as a catalyst for electrocatalytic water oxidation. The end component Co3Sb4O6F6 was found to be most efficient, maintaining a current density of j = 10 mA cm(-2) at an overpotential of 443 mV with good capability. At this current density, O-2 and H-2 were produced in the ratio 1 : 2 without loss of faradaic current against a Pt-cathode. A morphological change in the crystallite surface was observed after 0.5 h, however, even after 64.5 h, the overall shape and size of the small crystallites were unaffected and the electrolyte contained only 0.02 at% Co. It was also possible to conclude from in situ EXAFS measurements that the coordination around Co did not change. The oxofluorides express both hydrophilic and hydrophobic surface sites, incorporate a flexible metalloid element and offer the possibility of a mechanism that differs from other inorganic catalytic pathways previously described.

The application of the recently discovered oxofluoride solid solution (CoxNi1-x)(3)Sb4O6F6 as a catalyst for water oxidation is demonstrated. The phase exhibits a cubic arrangement of the active metal that forms oxo bridges to the metalloid with possible catalytic participation. The Co3Sb4O6F6 compound proved to be capable of catalyzing 2H(2)OO(2)+4H(+)+4e(-) at 0.33V electrochemical and 0.39V chemical overpotential with a TOF of 4.410(-3), whereas Ni3Sb4O6F6 needs a higher overpotential. Relatively large crystal cubes (0.3-0.5mm) are easily synthesized and readily handled as they demonstrate both chemical resistance to wear after repeated insitu tests under experimental conditions, and have a mechanical hardness of 270V0.1 using Vickers indentation. The combined properties of this compound offer a potential technical advantage for incorporation to a catalytic interface in future sustainable fuel production.

Herein, we describe the use of Pd nanoparticles immobilized on an amino-functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four-electron oxidation of H2O to O-2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar-fuel production.

Two new oxohalides Co₄Se₃O₉Cl₂ and Co₃Se₄O₁₀Cl₂ have been synthesized by solid state reactions. They crystallize in the orthorhombic space group Pnma and the monoclinic space group C2/m respectively. The crystal structure of the two compounds are made up of similar building blocks; Co₄Se₃O₉Cl₂ is made up of [CoO₄Cl₂], [CoO₅Cl] and [SeO₃] polyhedra and Co₃Se₄O₁₀Cl₂ is made up of [CoO₄Cl₂] and [SeO₃] polyhedra. As several Co-containing compounds have proved to be good catalysts for water oxidation, the activities of the two new compounds were compared with the previously found oxohalide Co₅Se₄O₁₂Cl₂ in reference to CoO and CoCl₂. The one electron oxidant Ru(bpy)₃³⁺ was used as oxidizing species in a phosphate buffer and it was found that the activities of the oxohalide species were in between CoO and CoCl₂. The roles of Cl⁻ and PO₄³⁻ ions are discussed.