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Abstract: CeOs 4 Sb 12 (COS) and PrOs 4 Sb 12 (POS) are two representative compounds that provide the ideal vantage point to systematically study the physics of multi- f -electron systems. COS with Ce 4 f 1 , and POS with Pr 4 f 2 configurations show distinct properties of Kondo insulating and heavy fermion superconductivity, respectively. We unveiled the underlying microscopic origin by angle-resolved photoemission spectroscopy studies. Their eV-scale band structure matches well, representing the common characters of conduction electrons in R Os 4 Sb 12 systems ( R = rare   earth ). However, f electrons interact differently with conduction electrons in COS and POS. Strong hybridization between conduction electrons and f electrons is observed in COS with band dependent hybridization gaps, and the development of a Kondo insulating state is directly revealed. Although the ground state of POS is a singlet, finite but incoherent hybridization exists, which can be explained by the Kondo scattering with the thermally excited triplet crystalline electric field state. Our results help us to understand the intriguing properties in COS and POS, and provide a clean demonstration of the microscopic differences in heavy fermion systems with 4 f 1 and 4 f 2 configurations.

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Abstract: Mixed metal oxides are important catalysts in industrial processes that transform bulk hydrocarbons into useful intermediates and products. The oxygen lattice is uniquely able to facilitate redox reactions by rapidly transporting reactive species between active sites. The bulk structure of the lattice governs the availability of electrons, the reactivity of oxygen, and hence the efficiency of catalytic processes. An in-depth understanding of catalyst structure and formation mechanisms is therefore key to the development of effective catalysts. The study of relatively simple oxides gives fundamental knowledge that cannot always be applied to the more complex mixed metal oxide systems that are patented and put into use industrially. The goal of this research is to apply fundamental techniques to complex, commercial catalysts, under industrially relevant conditions, and systematically make sense of the complexity. A range of characterisation techniques that probe different aspects of catalyst structure are used in this thesis during catalyst synthesis to follow (re)organisation pathways of mixed metal oxides and identify the different structures that form. Two mixed metal oxide systems were chosen for investigation: a Cu-spinel based hydrogenation catalyst and a Mo oxide selective oxidation catalyst. The structural transformations during different synthesis steps were analysed using X-ray Absorption Spectroscopy (XAS), X-ray Diffraction (XRD), Infrared (IR), and Raman spectroscopy. New insights into both catalyst systems are discussed and several approaches to catalyst characterisation on different length scales are demonstrated to deliver a holistic understanding of catalyst synthesis.

Open Access

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Abstract: A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3O7F and TaO2F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3O7F and TaO2F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering equipment. iv) SPS processing changes the catalytic properties: while conventionally prepared Ta3O7F and TaO2F show little catalytic activity, SPS‐prepared Ta3O7F and TaO2F exhibit high activity for photocatalytic oxygen evolution, reaching photoconversion efficiencies up to 24.7% and applied bias to photoconversion values of 0.86%. This study shows that the materials properties are dictated by the processing which poses new challenges to understand and predict the underlying factors.

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Abstract: Despite their ubiquitous usage and increasing societal dependence on Li-ion batteries, there remains a lack of detailed empirical evidence of Li intercalation/deintercalation into graphite even though this process dictates the performance, longevity, and safety of the system. Here, we report direct detection and dissociation of specific crystallographic phases in the lithiated graphite, which form through a stepwise staging process. Using operando measurements, LiC18, LiC12, and LiC6 phases are observed via distinct low-frequency Raman features, which are the result of displacement of the graphite lattice by induced local strain. Density functional theory calculations confirm the nature of the Raman-active vibrational modes, to the layer breathing modes (LBMs) of the lithiated graphite. The new findings indicate graphene-like characteristics in the lithiated graphite under the deep charged condition due to the imposed strain by the inserted Li. Moreover, our approach also provides a simple experimental tool to measure induced strain in the graphite structure under full intercalation conditions.

Open Access

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Abstract: The very-long-chain fatty acyl-CoA synthetase FadD13 from Mycobacterium tuberculosis activates fatty acids for further use in mycobacterial lipid metabolism. FadD13 is a peripheral membrane protein, with both soluble and membrane-bound populations in vivo. The protein displays a distinct positively charged surface patch, suggested to be involved in membrane association. In this paper, we combine structural analysis with liposome co-flotation assays and membrane association modeling to gain a more comprehensive understanding of the mechanisms behind membrane association. We show that FadD13 has affinity for negatively charged lipids, such as cardiolipin. Addition of a fatty acid substrate to the liposomes increases the apparent affinity of FadD13, consistent with our previous hypothesis that FadD13 can utilize the membrane to harbor its very-long-chain fatty acyl substrates. In addition, we unambiguously show that FadD13 adopts a dimeric arrangement in solution. The dimer interface partly buries the positive surface patch, seemingly inconsistent with membrane binding. Notably, when cross-linking the dimer, it lost its ability to bind and co-migrate with liposomes. To better understand the dynamics of association, we utilized two mutant variants of FadD13, one in which the positively charged patch was altered to become more negative and one more hydrophobic. Both variants were predominantly monomeric in solution. The hydrophobic variant maintained the ability to bind to the membrane, whereas the negative variant did not. Taken together, our data indicate that FadD13 exists in a dynamic equilibrium between the dimer and monomer, where the monomeric state can adhere to the membrane via the positively charged surface patch.