The structure and catalytic aspects of tungsten bronzes have been considered. A series of potassium tungsten bronzes, KxW03, 0.05 =< x =< 0.8, and the corresponding series of sodium tungsten bronzes, NaxW03, 0.05 =< x =< 0.8 were prepared by a thermal method. The thermal stability of the prepared samples was studied in the presence of both an oxidising and a reducing gas. The number and strength of acid sites present on the bronzes was studied by temperature-programmed desorption of ammonia. Xps, xrd and electrical resistivity measurements gave information about the bulk and surface properties of the bronzes. The activity of the tungsten bronzes for isopropanol decomposition and propene metathesis was investigated. In addition, a silica-supported tungsten bronze and a copper-potassium tungsten bronze, CUyKxW03, were prepared. Their structures and catalytic values were considered.

No description available.

[EN] The project of this Ph.D. thesis is based on a co-supervised collaboration between Università di Bologna, ALMA MATER STUDIORUM (Italy) and Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (Spain). This Ph.D. thesis is about the synthesis, characterization and catalytic testing of complex mixed-oxide catalysts mainly related to the family of Hexagonal Tungsten Bronzes (HTBs). These materials have been little explored as catalysts, although they have a great potential as multifunctional materials. Their peculiar acid properties can be coupled to other functionalities (e.g. redox sites) by isomorphous substitution of tungsten atoms with other transition metals such as vanadium, niobium and molybdenum. In this PhD thesis, it was demonstrated how it is possible to prepare substituted-HTBs by hydrothermal synthesis; these mixed-oxide were fully characterize by a number of physicochemical techniques such as XPS, HR-TEM, XAS etc. They were also used as catalysts for the one-pot glycerol oxidehydration to acrylic acid; this reaction might represent a viable chemical route to solve the important issue related to the co-production of glycerin along the biodiesel production chain. Acrylic acid yields as high as 51% were obtained and important structure-reactivity correlations were proved to govern the catalytic performance; only fine tuning of acid and redox properties as well as the in-framework presence of vanadium are fundamental to achieve noteworthy yields into the acid monomer. The overall results reported herein might represent an important contribution for future applications of HTBs in catalysis as well as a general guideline for a multifaceted approach for their physicochemical characterization. / [ES] El proyecto de esta tesis doctoral está basado en un convenio de cotutela firmado por la Università di Bologna, ALMA MATER STUDIORUM (Italia) y el Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (España). La presente tesis doctoral muestra el estudio sobre la síntesis, caracterización y ensayos catalíticos de materiales complejos a base de óxidos mixtos relacionados con la familia de los bronces de tungsteno hexagonales. Estos materiales han sido utilizados minoritariamente como catalizadores, aunque tienen un potencial importante come materiales multifuncionales. Sus peculiares propiedades acidas pueden ser acopladas con otras características (por ejemplo, sitios oxido-reductivos) a través de la substitución isomórfica de átomos de tungsteno con otros metales de transición como vanadio, niobio y molibdeno. En esta tesis doctoral se ha demostrado como sea posible preparar bronces de tungsteno hexagonales substituidos a través de síntesis hidrotermal; estos óxidos mixtos fueron caracterizados por completo empleando numerosas técnicas de caracterización quimico-fisicas como XPS, HR-TEM, XAS etc. Fueron también utilizados como catalizadores para la síntesis directa de acido acrílico de glicerol; esta es una reacción que puede representar una solución viable para el problema relacionado con la coproducción de glicerina a lo largo de la cadena productiva del biodiesel. Rendimientos en acido acrílico hasta el 51% fueron obtenidos y importantes relaciones entre las estructuras y la actividad catalítica fueron demostradas ser determinantes para el proceso catalítico; solo la afinación de las propiedades acidas y redox tanto como la presencia en-red de vanadio son esenciales para conseguir rendimientos relevantes en el monómero acido. En general, los resultados presentados en esta tesis doctoral pueden ser una contribución relevante para futuras aplicaciones de los bronces de tungsteno hexagonales en catálisis y también como una guía general para un completa caracterización quimico-fisica de estos oxidos. / [CAT] Esta tesi doctoral està basada en un conveni de cotutela signat per la Università di Bologna, ALMA MATER STUDIORUM (Italia) i el Institut de Tecnologia Química , Universitat Politècnica de València ITQ-UPV(Espanya). La present tesi doctoral estudia la síntesis, caracterització i assajos catalítics de òxids mixtes relacionats amb la família dels bronzes de tungstèn hexagonals. Aquestos materials presenten un gran potencial com materials multi funcionals, encara que no han sigut molt emprats com catalitzadors. Les propietats àcides particulars de aquestos materials poden ser potenciades amb altres característiques (per exemple, llocs redox) mitjançant la substitució isomòrfica d'àtoms de tungstèn amb altres metalls de transició com vanadi, niobi i molibdè. En aquesta tesi doctoral es demostra com es possible sintetitzar bronzes de tungstèn hexagonals substituïts a partir de síntesis hidrotermal. Aquestos òxids mixtes han segut caracteritzats emprant diverses tècniques de caracterització físico-químiques com XPS, HR-TEM, XAS, etc... Per altra part, s'han utilitzat com catalitzadors per a la síntesis directa de àcid acrílic a partir de glicerol, aquesta reacció pot representar una solució viable per al problema relacionat amb la coproducció de glicerina al llarg de la cadena productiva de biodiesel. S'han obtingut rendiments a àcid acrílic del 51%. A més, s'han observat importants relacions entre les estructures i la activitat catalítica, les quals han sigut determinants per al procés catalític. El ajust de les propietats àcides i redox i la presència en red de vanadi són essencials per a obtindre rendiments rellevants en el monòmer àcid. En general, el resultats presentats en aquesta tesi doctoral poden ser una contribució rellevant per a futures aplicacions del bronzes de tungstèn hexagonal en catàlisis i també com una guia general per a una completa caracterització físico-química d'aquestos òxids. / Chieregato, A. (2015). Glycerol oxidehydration to acrylic acid on complex mixed-metal oxides [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/49558 / TESIS

In this work, in-depth structural and electrical characterisation is used to study a family of “empty” tetragonal tungsten bronzes (TTBs), A2₄A1₂B1₂B2₈O₃₀. An initial investigation into the effect of the A1-cation size on the properties of empty Ba₄R₀.₆₇◻₁.₃₃Nb₁₀O₃₀ TTBs (where R is the A1-cation and R = La, Nd, Sm, Gd, Dy and Y; ◻ = vacancy) was performed. These were determined to be metrically tetragonal by powder x-ray diffraction, with decreasing R cation size inducing increased crystal anisotropy. This tetragonal structural distortion, driven by contraction in the ab-plane, is shown to stabilise c-axis ferroelectricity; a direct correlation between tetragonality and the ferroelectric Curie temperature, T[sub]C, is demonstrated. Further examination of the relaxor ferroelectric (RFE) to ferroelectric (FE) crossover in Ba₄(La₁₋ₓNdₓ)₀.₆₇◻₁.₃₃Nb₁₀O₃₀ TTBs using detailed structural studies employing variable temperature, high resolution neutron, synchrotron X-ray and electron diffraction revealed a common superstructure with 2√2 × √2 × 2 cell with respect to the basic tetragonal aristotype cell. However, they display different degrees of order/disorder which can disrupt polar order (ferroelectricity). La-rich analogues exhibit a disordered regime between the low and high temperature ferroelectric and non-polar phases. Although polar, this disordered regime is non-ferroelectric, however, large polarisation may be established with an applied electric field, but relaxes back to the disordered phase upon removal of the field. Substitution of Nd for La at the A1-site leads to destabilisation of the disordered phase and reintroduces “normal” ferroelectric behaviour. Finally, isovalent substitution of Sr²⁺∙ for Ba²⁺ is shown to lead to the development of relaxor behaviour at higher dopant concentrations in Ba₄₋ₓSrₓDy₀.₆₇◻₁.₃₃Nb₁₀O₃₀, (x = 0, 0.25, 0.5, 1, 2, 3; ◻ = vacancy). With increasing x the unit cell contracts in both the ab- plane and c-axis coinciding with a decrease in T[sub]C and development of relaxor behaviour for x ≥ 2. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr²⁺ principally occupies the A2-site while for x ≥ 2 significant Sr²⁺ occupation of the A1-site leads to the observed RFE characteristics. The FE to RFE crossover is discussed in the context of a previously proposed TTB crystal chemical framework with the A1-site tolerance factor identified as the dominant influence on relaxor behaviour.

Transition metal fluorides represent an important family of complex solids displaying a variety of different properties and interesting phenomena. Despite their remarkable behaviour, these classes of materials have not received much attention and the rationalization of their behaviour is still lacking a systematic approach. This thesis aims to contribute to the field by examining previously unknown or understudied complex fluorides. The compounds were selected for their intriguing physical properties that range from superconductivity to multiferroism. The discovery of superconductivity in the iron pnictides sparked new interest in materials with layered ZrCuSiAs-type structure. Herein the properties of one of these systems, namely SrFeAsF, will be discussed. We have found that it behaves as a poor metal and undergoes a tetragonal (P4/nmm) to orthorhombic (Cmma) structural transition at T = 180 K, accompanied by a spin density wave in magnetic susceptibility and electrical resistivity. Below T < 150 K, the Fe moments order in antiferromagnetic spin-stripes. Electron doping with La3+ is a successful route to obtain superconducting phases, with maximum Tc = 27 K (x = 0.2). The isostructural AeMnPnF series (Ae = Sr, Ba; Pn = P, As, Sb) was also investigated to elucidate the influence of transition metal d-electrons and size effects of Ae and Pn on the physical properties. The isoelectronic replacement of Ae and Pn leads to a significant distortion in the tetragonal building blocks. All d5 Mn fluorides investigated here are insulating antiferromagnets with TN ~ 350 K. Due to the coexistence of electronic and magnetic ordering, the tetragonal tungsten bronze (TTB) materials KxM2+ xM3+ 1-xF3 (x = 0.4 – 0.6; M = transition metal) are potential multiferroics. The type of structural distortion adopted by these systems is strongly dependant on the M2+/M3+ ratio. For instance, our high-resolution diffraction study on K0.5Mn0.5Cr0.5F3 has revealed a small orthorhombic distortion, which indicates full chemical order of Mn2+ and Cr3+ on all crystallographic sites. K0.5Mn0.5Cr0.5F3 remains orthorhombic Ccc2 on cooling through the ferromagnetic transition at TN = 23 K. On heating, the structure is acentric up to T = 373 K, where a change to tetragonal P42/mbc symmetry marks the transition from ferroelectric (polar) to paraelectric (apolar) states. High-pressure diffraction experiments have shown that the Ccc2 structure is robust upon pressurization with anisotropic axial compressibility up to the maximum pressure applied p = 18 GPa. The crystal structure of related mixed-valence TTB fluoride K0.6Cr2+ 0.6Cr3+ 0.4F3 is influenced by the presence of Jahn-Teller active Cr2+. The structural analysis described here revealed the presence of a small polar monoclinic distortion (P112) providing a clear signature of full charge order (CO). On heating, the gradual loss of CO leads to two consecutive structural phase transitions to orthorhombic (Pba2, T = 423 K) and then tetragonal (P42/mbc, T = 823 K) lattices, the latter is the signature of the ferro- to paraelectric transition. Below T = 150 K, increased X-ray exposure time leads to CO-melting and the stabilization of a new, charge-disordered orthorhombic phase (Cmm2), with a phenomenology similar to the CO manganites. In highpressure diffraction experiments, a further transition to tetragonal P4bm symmetry is found at p = 6 GPa. The magnetic susceptibility points towards a complex spin arrangement, with two transitions at TN = 33 K and 6 K. The results presented herein show the richness of the structural, electronic and magnetic phase diagrams of transition metal fluorides and clearly demonstrate that systematic studies on these systems will greatly enhance our current understanding of the underlying mechanisms of important phenomena such as superconductivity and ferroelectricity.

Metal-insulator transition is one of the most important properties observed in certain materials which has been studied widely using a wide range of experimental techniques as well as theoretical models. This kind of a transition, observed in several systems, can take place by tuning several parameters such as pressure, temperature or the composition itself. In this thesis we study a few selected transition metal oxide bronzes exhibiting such phenomenon, each of which has a different cause for undergoing the transition. In Chapter 1, we discuss briefly several mechanisms and models that have been used to understand metal-insulator transitions. We also briefly discuss the role of disorder, electron-electron correlations or both to understand the different ways in which such transitions can occur. In Chapter 2, we describe the different experimental as well as theoretical techniques that have been used in this thesis. In Chapter 3, we study the fermi-edge of the NaxWO3 systems, as a function of x, to understand the origin of the metal-insulator transition occurring in this series of compounds. The system undergoes a metal-insulator transition at the critical composition xc=0.25, below which it is found to be insulating. At the lowest temperature, the very low x compounds behave as disordered and correlated materials. Above the transition composition, the compounds behave as disordered and correlated metals. In the insulating regime, close to the critical composition, we find that the system behaves in a way that cannot be described by any known theories for metals or insulators. We have also done a systematic analysis of the Fermi-edge data for the insulating samples as a function of temperature and we find that they cannot be described by any of the known theories for solid-state systems. Further development is necessary in the theoretical side to understand and interpret our data. In Chapter 4, we study the angle-resolved photoemission data for the highly metallic sodium tungsten bronze Na0.8WO3. We have synthesized the single-crystals by high-temperature electrochemical synthesis and we have performed angle-resolved photoemission experiments to understand the band structure of this system. The experimental results have been supported by theoretical calculations. We find that the rigid band model is valid in describing the electronic structure in these systems. We also find the existence of electron-like pockets along certain symmetry directions. Further, photon energy dependent studies on the x=0.8 sample suggest that there is a difference in the surface with the bulk of the sample. The bulk is perfectly periodic and ordered, whereas the surface shows a distortion due to the rotation or deformation of the WO6 octahedra. In Chapter 5, we have studied the electronic structure of the low dimensional molybdenum oxide La2Mo2O7, which is expected to have a charge density wave(CDW)driven metal-insulator transition around 125K. We indeed observed the presence of CDWs in this system, which was observed in the angle-resolved photoemission spectra as back-folding of bands below the transition temperature. We have also studied the temperature evolution of the bands close to the Fermi level and we see a gradually weakening and finally disappearance of the back-folded bands close to and above the transition temperature. We have studied the angle-integrated spectra of this system from which we conclude that La2Mo2O7 is a CDW non-Fermi liquid system. We have also evaluated the total and partial density of states in this system using Vienna ab-initio simulation package. We find the results consistent with our experimental findings. In Chapter 6, we study the metal-insulator transition in another low-dimensional molybdenum oxide KMo4O6, which is expected to show a metal-insulator transition around 120K due to the formation of spin-density waves. We observed back-folding of bands with lower intensities at low temperature, suggesting the formation of spin density waves in the system. The angle-integrated spectra suggested that the system is a non-CDW non-Fermi liquid system. We have also evaluated the density of states and the results are in agreement with our experimental findings. In conclusion we have investigated the electronic structure of different classes of systems and we have given clue to the origin of the metal-insulator transition in these systems.

There is great interest in the development of new polar dielectric ceramics and multiferroic materials with new and improved properties. A family of tetragonal tungsten bronze (TTB) relaxors of composition Ba₆M³⁺Nb₉O₃₀ (M³⁺ = Ga³⁺, Sc³⁺ and In³⁺, and also their solid solutions) were studied in an attempt to understand their dielectric properties to enable design of novel polar TTB materials. A combination of electrical measurements (dielectric and impedance spectroscopy) and powder diffraction (X-ray and neutron) studies as a function of temperature was employed for characterising the dynamic dipole response in these materials. The effect of B-site doping on fundamental dipolar relaxation parameters were investigated by independently fitting the dielectric permittivity to the Vogel-Fulcher (VF) model, and the dielectric loss to Universal Dielectric Response (UDR) and Arrhenius models. These studies showed an increase in the characteristic dipole freezing temperature (T[subscript(f)]) with increase B-cation radius. Crystallographic data indicated a corresponding maximum in tetragonal strain at T[subscript(f)], consistent with the slowing and eventual freezing of dipoles. In addition, the B1 crystallographic site was shown to be most active in terms of the dipolar response. A more in-depth analysis of the relaxor behaviour of these materials revealed that, with the stepwise increase in the ionic radius of the M³⁺ cation on the B-site within the Sc-In solid solution series, the Vogel-Fulcher curves (lnf vs. T[subscript(m)]) are displaced to higher temperatures, while the degree of relaxor behaviour (frequency dependence) increases. Unfortunately, additional features appear in the dielectric spectroscopy data, dramatically affecting the Vogel-Fulcher fitting parameters. A parametric study of the reproducibility of acquisition and analysis of dielectric data was therefore carried out. The applicability of the Vogel-Fulcher expression to fit dielectric permittivity data was investigated, from the simple unrestricted (“free”) fit to a wider range of imposed values for the VF relaxation parameters that fit with high accuracy the experimental data. The reproducibility of the dielectric data and the relaxation parameters obtained by VF fitting were shown to be highly sensitive to the thermal history of samples and also the conditions during dielectric data acquisition (i.e., heating/cooling rate). In contrast, UDR analysis of the dielectric loss data provided far more reproducible results, and to an extent was able to partially deconvolute the additional relaxation processes present in these materials. The exact nature of these additional relaxations is not yet fully understood. It was concluded application of the Vogel-Fulcher model should be undertaken with great care. The UDR model may represent a feasible alternative to the evaluation of fundamental relaxation parameters, and a step forward towards the understanding of the dielectric processes in tetragonal tungsten bronzes.

There has been an increase in the interest in fluoride materials over the last decade. This interest has focused on multiferroic materials and kagome lattices, to name but a few areas. This thesis focuses on the synthesis and crystallographic characterisation of selected transition metal fluorides and oxyfluorides. Work is presented on the tetragonal tungsten bronze solid solutions of KₓFeF₃, where x = 0.58 and x ≈ 0.5, and the copper analogue, K₃Cu₃Fe₂F₁₅; the kagome structure of Cs₂ZrCu₃F₁₂; and hydrothermal reactions using vanadium, manganese, or molybdenum as the transition metals in the formation of new fluorides and oxyfluorides. The tetragonal tungsten bronze compounds KₓFeF₃ (x = 0.58 and x ≈ 0.5) are both tetragonal at 500 K. In the variant with the lower K-content, there is a clear phase separation into two tetragonal phases even at this temperature. The K₀.₅₈FeF₃ sample separates into two distinct phases below 340 K to possess one tetragonal and one orthorhombic phase. Then at roughly 300 K, both samples undergo a phase transition where the tetragonal phase in the P4/mbm space group in K₀.₅₈FeF₃ changes to an orthorhombic phase with a larger unit cell; and the tetragonal phase in P4₂bc for the K₀.₅FeF₃ sample changes to the same orthorhombic model, whilst the P4/mbm model remains unchanged. The evolution of the lattice parameters and phase fractions is studied in detail using synchrotron powder X-ray diffraction (sPXRD). The kagome structure investigated, Cs₂ZrCu₃F₁₂, possesses the “ideal” kagome lattice at room temperature, but previous work has suggested that there is a phase transition at 225 K. The two structures are determined by single crystal X-ray diffraction at 300 K and 125 K. Variable temperature sPXRD studies are performed between these two temperature ranges to determine the phase evolution as a function of temperature. The structure changes from a rhombohedral to a monoclinic phase at low temperature. This is the result of the buckling of the kagome layers at the phase transition. The Zr⁴⁺ ion changes from 6 to 7 coordinate and this is seen as the main driving force for the distortion of the kagome layer from its “ideal” planar arrangement. ii The phase transition is first-order as seen from the electrical impedance measurements. The hydrothermal reactions presented reveal seven new materials and their crystal structures. Sr₂V₂F₁₀·H₂O is new and found to be isostructural to Sr₂Fe₂F₁₀·H₂O. BaVO₂F₃ is a cubic material that is potentially piezoelectric. Two hybrid organic inorganic manganese compounds are reported. The ladder structure (C₃N₂H₅)[Mn₂F₆(H₂O)₂] crystallises in a polar space group and shows promise as a candidate for multiferroic studies. The second hybrid material, (C₇NH₁₆)₂[MnF₅(H₂O)]·2H₂O, crystallises in a centrosymmetric space group. The Mo hybrid materials are all centrosymmetric and possess isolated molybdenum-centred monomeric or dimeric octahedral units.

Les travaux présents ici portent sur l’étude et la prospection de matériaux ferroiques. Cette étude consiste en une approche revêtant plusieurs aspects que sont la chimie du solide, la physique du solide et la science des matériaux. Deux parties sont développées, avec deux approches différentes. La première se concentre sur les liens entre composition/structure/propriétés dans des matériaux de la famille des TTB dérives de Ba2NdFeNb4O15 à travers l’étude de solutions solides à base de Li et l’étude de l’impact des différents paramètres de synthèse sur la nature de l’anomalie diélectrique mesurées sur pastilles densifiées. La mise en évidence de modulation structurale dans cette famille de matériaux semble être en lien direct avec l’observation des variations de propriétés diélectriques. L’utilisation de diffraction électronique notamment permet la mise en évidence de ces modulations structurales et leur évolution en température. Dans une seconde partie, l’approche consiste à utiliser le Spark Plasma Sintering (SPS) comme technique de densification pour des matériaux dits “fragiles” mais aussi d’explorer des propriétés diélectriques jusqu’alors inaccessibles, sur matériaux massifs. Le développement de la technique SPS à basse température permet ainsi non seulement de densifier à basse température des matériaux fragiles, mais aussi d’obtenir des phases inaccessibles dans des conditions de températures similaires par traitement thermique conventionnel. De même, l’obtention de céramique moléculaire de très haute densité a pu être réalisée, malgré des températures de décomposition extrêmement faible (100 ˚C). / The present work focuses on the prospection and understanding study of ferroic materials. It consists in a multiple aspect approach, including materials chemistry, materials physics and materials processing. Two parts compose this work, with two different approaches. The first one focuses on the links between composition, structure and properties in materials belonging to the TTB family, more specifically derived from Ba2NdFeNb4O15, through the exploration of Li containing solid solutions, and the impact of synthesis parameters on measured dielectric anomalies on dense samples. The observation of structural modulation in these materials seems to be closely related to the observation of dielectric anomalies variations. Using electron diffraction techniques allowed the evidence of such anomalies and the following of their thermal evolution. In a second part, the approach consists in using Spark Plasma Sintering (SPS) as a densification technique for so called “fragile” materials but also explore dielectric properties impossible to experimentally measure thus far. Developing low temperature SPS technique not only allows to densify ceramics at low temperatures fragile materials, but also to obtain inaccessible phases in similar temperature conditions using conventional thermal treatments. Moreover, sintering of molecular ceramic at very high density was possible, even if its decomposition temperature is extremely low (100 ˚C).

Übergangsmetalloxidbronzen (TMOB) – Verbindungen mit der allgemeinen chemischen Summenformel AxByOz (A = Element der Gruppen 1, 2, 11, 12, 13, NH4+ oder Kombination; B = Übergangsmetall) – sind seit längerem als Material für ionensensitive Festkörperelektroden bekannt. Sie reagieren als Elektroden in elektrochemischen Messungen auf Ionen in wässrigen Elektrolyten in höchst unterschiedlicher Weise. Bis heute gibt es dazu nur wenige systematische vergleichende Untersuchungen, die von der Präparation der Bronzen, der Charakterisierung ihrer Eigenschaften bis zur Untersuchung ihrer Elektrodeneigenschaften reichen. Gegenstand der Arbeit war deshalb die Synthese von in der Literatur beschriebenen TMOB auf der Basis von Wolfram und Molybdän, die Bestimmung ihrer Kristallstruktur und die Untersuchung ihrer chemischen und physikalischen Eigenschaften. Aus den synthetisierten Verbindungen waren anhand einer elektrochemischen Vorcharakterisierung einige auszuwählen, um diese systematisch als Elektroden zu untersuchen. Insbesondere HxMoO3, Ba0,12WO3 und Li0,4Mo0,95W0,05O3 zeichneten sich durch gegenüber den anderen Oxidbronzen abweichende potentiometrische Charakteristika aus. Hinsichtlich der Einsetzbarkeit dieser Materialien für potentiometrische Elektroden wurden diese Verbin¬dungen noch nicht untersucht. Daher wurden diese Verbindungen eingehender erforscht. Die bezüglich ihrer potentiometrischen Eigen¬schaften bereits ausreichend untersuchte Verbindung Na0,9Mo6O17 diente dem Vergleich und wurde deshalb den selben Tests ausgesetzt. Dazu waren im Einzelnen potentiometrische Messungen in Abhängigkeit von der Konzentration der Alkaliionen und der Wasserstoffionen sowie von der Konzentration verschiedener Redoxspezies in wässrigen Medien durchzuführen. Unklar war bisher wie sich die Wechselwirkungen der gelösten Ionen mit den Molybdän- und Wolframionen im Festkörper vollziehen und warum die Elektroden Sensitivitäten für verschiedene Ionen aufweisen, die sich nicht aus der chemischen Zusammensetzung oder mit der Kristallstruktur der jeweiligen Oxidbronze erklären lassen. Zur Aufhellung dieses Problems waren unter anderem XPS-Untersuchungen an verschiedenen Oxidbronzen durchzuführen, aus denen man auf den Oxidationszustand des Wolframs und Molybdäns im Festkörper schließen kann.