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Abstract: Tetrapodal zinc oxide (t-ZnO) is used to fabricate polymer composites for many different applications ranging from biomedicine to electronics. In recent times, macroscopic framework structures from t-ZnO have been used as a versatile sacrificial template for the synthesis of multi-scaled foam structures from different nanomaterials such as graphene, hexagonal boron nitride or gallium nitride. Many of these fabrication methods rely on wet-chemical coating processes using nanomaterial dispersions, leading to a strong interest in the actual coating mechanism and factors influencing it. Depending on the type of medium (e.g. solvent) used, different results regarding the homogeneity of the nanomaterial coating can be achieved. In order to understand how a medium influences the coating behavior, the evaporation process of water and ethanol is investigated in this work using in situ synchrotron radiation-based micro computed tomography (SRµCT). By employing propagation-based phase contrast imaging, both the t-ZnO network and the medium can be visualized. Thus, the evaporation process can be monitored non-destructively in three dimensions. This investigation showed that using a polar medium such as water leads to uniform evaporation and, by that, a homogeneous coating of the entire network.

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Abstract: We demonstrate that the interfacial dipole associated with bonding across the SrTi O 3 / Si heterojunction can be tuned through space charge, thereby enabling the band alignment to be altered via doping. Oxygen impurities in Si act as donors that create space charge by transferring electrons across the interface into SrTi O 3 . The space charge induces an electric field that modifies the interfacial dipole, thereby tuning the band alignment from type II to III. The transferred charge, accompanying built-in electric fields, and change in band alignment are manifested in electrical transport and hard x-ray photoelectron spectroscopy measurements. Ab initio models reveal the interplay between polarization and band offsets. We find that band offsets can be tuned by modulating the density of space charge across the interface. Modulating the interface dipole to enable electrostatic altering of band alignment opens additional pathways to realize functional behavior in semiconducting hybrid heterojunctions.

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Abstract: Hybridization of electronic states and orbital symmetry in transition metal oxides are generally considered key ingredients in the description of both their electronic and magnetic properties. In the prototypical case of La 0.65 Sr 0.35 MnO 3 (LSMO), a landmark system for spintronics applications, a description based solely on Mn 3 d and O 2 p electronic states is reductive. We thus analyzed elemental and orbital distributions in the LSMO valence band through a comparison between density functional theory calculations and experimental photoelectron spectra in a photon energy range from soft to hard x rays. We reveal a number of hidden contributions, arising specifically from La 5 p , Mn 4 s , and O 2 s orbitals, considered negligible in previous analyses; our results demonstrate that all these contributions are significant for a correct description of the valence band of LSMO and of transition metal oxides in general.

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Abstract: 2-Hydroxypropyl methacrylate (HPMA) is a useful model monomer for understanding aqueous dispersion polymerization. 4-Hydroxybutyl acrylate (HBA) is an isomer of HPMA: it has appreciably higher aqueous solubility so its homopolymer is more weakly hydrophobic. Moreover, PHBA possesses a significantly lower glass transition temperature than PHPMA, which ensures greater chain mobility. The reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of HBA using a poly(ethylene glycol) (PEG113) precursor at 30 °C produces PEG113–PHBA200–700 diblock copolymer nano-objects. Using glutaraldehyde to crosslink the PHBA chains allows TEM studies, which reveal the formation of spheres, worms or vesicles under appropriate conditions. Interestingly, the partially hydrated highly mobile PHBA block enabled linear PEG113–PHBAx spheres, worms or vesicles to be reconstituted from freeze-dried powders on addition of water at 20 °C. Moreover, variable temperature 1H NMR studies indicated that the apparent degree of hydration of the PHBA block increases from 5% to 80% on heating from 0 °C to 60 °C indicating uniform plasticization. In contrast, the PHPMAx chains within PEG113–PHPMAx nano-objects become dehydrated on raising the temperature: this qualitative difference is highly counter-intuitive given that PHBA and PHPMA are isomers. The greater (partial) hydration of the PHBA block at higher temperature drives the morphological evolution of PEG113–PHBA260 spheres to form worms or vesicles, as judged by oscillatory rheology, dynamic light scattering, small-angle X-ray scattering and TEM studies. Finally, a variable temperature phase diagram is constructed for 15% w/w aqueous dispersions of eight PEG113–PHBA200–700 diblock copolymers. Notably, PEG113–PHBA350 can switch reversibly from spheres to worms to vesicles to lamellae during a thermal cycle.

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Abstract: We demonstrate a modified sol-immobilization procedure using (MeOH) x /(H 2 O) 1-x solvent mixtures to prepare Pd/TiO 2 catalysts that are able to reduce the formation of acid catalyzed products, e.g. ethers, for the hydrogenation of furfural. Transmission electron microscopy found a significant increase in polyvinyl alcohol (PVA) deposition at the metal-support interface and temperature programmed reduction found a reduced uptake of hydrogen, compared to an established Pd/TiO 2 preparation. We propose that the additional PVA hinders hydrogen spillover onto the TiO 2 support and limits the formation of Brønsted acid sites, required to produce ethers. Elsewhere, the new preparation route was able to successfully anchor colloidal Pd to the TiO 2 surface, without the need for acidification. This work demonstrates the potential for minimizing process steps as well as optimizing catalyst selectivity – both important objectives for sustainable chemistry.