Marco Zanella

Catalytic Response and Stability of Nickel/Alumina for the Hydrogenation of 5-Hydroxymethylfurfural in Water.

The catalytic response of Ni on Al2O3 obtained from Ni-Al layered double hydroxides was studied for the liquid-phase hydrogenation of hydroxymethyl furfural to tetrahydrofuran-2,5-diyldimethanol (THFDM) in water. The successive calcination and reduction of the precursors caused the removal of interlayer hydroxyl and carbonate groups and the reduction of Ni(2+) to Ni(0). Four reduced mixed oxide catalysts were obtained, consisting of different amount of Ni metal contents (47-68 wt%) on an Al-rich amorphous component. The catalytic activity was linked to Ni content whereas selectivity was mainly affected by reaction temperature. THFDM was formed in a stepwise manner at low temperature (353 K) whereas 3-hydroxymethyl cyclopentanone was generated at higher temperature. Coke formation caused deactivation; however, the catalytic activity can be regenerated using heat treatment. The results establish Ni on Al2O3 as a promising catalyst for the production of THFDM in water.

Morphotropic Phase Boundary in the Pb‐Free (1 − x)BiTi3/8Fe2/8Mg3/8O3–xCaTiO3 System: Tetragonal Polarization and Enhanced Electromechanical Properties

Lead-free bismuth-based perovskite oxides with polarization directed along the [001](p) primitive perovskite unit cell edge, analogous to tetragonal PbTiO3, are synthesized at ambient pressure. Enhanced piezoelectric properties, large polarizations, and high depolarization temperatures are observed in the wide morphotropic phase boundary region formed with a rhombohedral phase, with up to 92.5% Bi on the perovskite A site.

Selective conversion of 5-hydroxymethylfurfural to cyclopentanone derivatives over Cu–Al2O3 and Co–Al2O3 catalysts in water

The production of cyclopentanone derivatives from 5-hydroxymethylfurfural (HMF) using non-noble metal based catalysts is reported for the first time. Five different mixed oxides containing Ni, Cu, Co, Zn and Mg phases on an Al-rich amorphous support were prepared and characterised (XRD, ICP, SEM, TEM, H2-TPR, NH3/CO2-TPD and N2 sorption). The synthesised materials resulted in well-dispersed high metal loadings in a mesoporous network, exhibiting acid/base properties. The catalytic performance was tested in a batch stirred reactor under H2 pressure (20–50 bar) in the range T = 140–180 °C. The Cu–Al2O3 and the Co–Al2O3 catalysts showed a highly selective production of 3-hydroxymethylcyclopentanone (HCPN, 86%) and 3-hydroxymethylcyclopentanol (HCPL, 94%), respectively. A plausible reaction mechanism is proposed, clarifying the role of the reduced metal phases and the acid/basic sites on the main conversion pathways. Both Cu–Al2O3 and Co–Al2O3 catalysts showed a loss of activity after the first run, which can be reversed by a regeneration treatment. The results establish an efficient catalytic route for the production of the diol HCPL (reported for the first time) and the ketone HCPN from bio-derived HMF over 3d transition metals based catalysts in an environmental friendly medium such as water.

Accelerated discovery of two crystal structure types in a complex inorganic phase field

The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large number of possible elemental compositions for such materials, and of the candidate structures at each composition. For example, the discovery of inorganic extended solid structures has relied on knowledge of crystal chemistry coupled with time-consuming materials synthesis with systematically varied elemental ratios. Computational methods have been developed to guide synthesis by predicting structures at specific compositions and predicting compositions for known crystal structures, with notable successes. However, the challenge of finding qualitatively new, experimentally realizable compounds, with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge. Here we report the experimental discovery of two structure types by computational identification of the region of a complex inorganic phase field that contains them. This is achieved by computing probe structures that capture the chemical and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent experimental exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them.

Room Temperature Magnetically Ordered Polar Corundum GaFeO3 Displaying Magnetoelectric Coupling

The polar corundum structure type offers a route to new room temperature multiferroic materials, as the partial LiNbO3-type cation ordering that breaks inversion symmetry may be combined with long-range magnetic ordering of high spin d5 cations above room temperature in the AFeO3 system. We report the synthesis of a polar corundum GaFeO3 by a high-pressure, high-temperature route and demonstrate that its polarity arises from partial LiNbO3-type cation ordering by complementary use of neutron, X-ray, and electron diffraction methods. In situ neutron diffraction shows that the polar corundum forms directly from AlFeO3-type GaFeO3 under the synthesis conditions. The A3+/Fe3+ cations are shown to be more ordered in polar corundum GaFeO3 than in isostructural ScFeO3. This is explained by DFT calculations which indicate that the extent of ordering is dependent on the configurational entropy available to each system at the very different synthesis temperatures required to form their corundum structures. Polar corundum GaFeO3 exhibits weak ferromagnetism at room temperature that arises from its Fe2O3-like magnetic ordering, which persists to a temperature of 408 K. We demonstrate that the polarity and magnetization are coupled in this system with a measured linear magnetoelectric coupling coefficient of 0.057 ps/m. Such coupling is a prerequisite for potential applications of polar corundum materials in multiferroic/magnetoelectric devices.

Luminescent Solar Concentrators utilising aligned CdSe/CdS nanorods

Luminescent Solar Concentrators (LSCs) were originally proposed in the 1970s as a means to reduce the cost of solar energy. LSCs typically consist of a transparent substrate made from PMMA or glass, homogeneously doped with a luminescent species, with solar cells coupled to the edge(s). In this paper CdSe/CdS core/shell nanorods (NRs) are utilized as the luminescent species within luminescent solar concentrator. NRs can be tuned to absorb and emit at different wavelengths by controlling their radial and length dimensions, varying quantum confinement. Additionally, NRs can be aligned, which can reduce light cone losses. The luminescent quantum yield (LQY) of the CdSe/CdS nanorods was found to be unaffected by the high density of nanorods required for alignment, the LQY was measured as 72.4±5% which compares well with literature values. Absorptivity measurements were used to determine that the majority of the nanorods within the thin-film were vertically aligned, with the exception of the nanorods at the edge of the thin-film. The sample was found to have considerably lower absorptivity in the central region, consistent with the presence of vertically aligned CdSe/CdS nanorods which have lower absorptivity in this particular orientation. Finally, the samples optical efficiency was measured to be 7.4±0.5%, which is more than a factor of two higher than the computational derived value of 3.17±0.19% which assumes the CdSe/CdS nanorods emit isotropically.

Utilizing vertically aligned CdSe/CdS nanorods within a luminescent solar concentrator

Optical characterisation methodologies are employed to validate a nanorod self-alignment technique for use in luminescent solar concentrators (LSCs). The nanorods utilised in this work were CdSe/CdS core/shell nanorods, and the self-alignment technique relied on the evaporation of a highly concentrated nanorod/xylene solution onto a glass substrate. Position and angular dependent light absorptivity measurements revealed evidence of vertical nanorod alignment over a limited region at the centre of the LSC sample. Vertical nanorod alignment is beneficial for absorbing diffuse/scattered sunlight and provides for a high light trapping efficiency in the LSC.

Bi4O4Cu1.7Se2.7Cl0.3: Intergrowth of BiOCuSe and Bi2O2Se Stabilized by the Addition of a Third Anion

Layered two-anion compounds are of interest for their diverse electronic properties. The modular nature of their layered structures offers opportunities for the construction of complex stackings used to introduce or tune functionality, but the accessible layer combinations are limited by the crystal chemistries of the available anions. We present a layered three-anion material, Bi4O4Cu1.7Se2.7Cl0.3, which adopts a new structure type composed of alternately stacked BiOCuSe and Bi2O2Se-like units. This structure is accessed by inclusion of three chemically distinct anions, which are accommodated by aliovalently substituted Bi2O2Se0.7Cl0.3 blocks coupled to Cu-deficient Bi2O2Cu1.7Se2 blocks, producing a formal charge modulation along the stacking direction. The hypothetical parent phase Bi4O4Cu2Se3 is unstable with respect to its charge-neutral stoichiometric building blocks. The complex layer stacking confers excellent thermal properties upon Bi4O4Cu1.7Se2.7Cl0.3: a room-temperature thermal conductivity (κ) of 0.4(1) W/mK was measured on a pellet with preferred crystallite orientation along the stacking axis, with perpendicular measurement indicating it is also highly anisotropic. This κ value lies in the ultralow regime and is smaller than those of both BiOCuSe and Bi2O2Se. Bi4O4Cu1.7Se2.7Cl0.3 behaves like a charge-balanced semiconductor with a narrow band gap. The chemical diversity offered by the additional anion allows the integration of two common structural units in a single phase by the simultaneous and coupled creation of charge-balancing defects in each of the units.

CdSe/CdS nanorods-polymer nanocomposites patternable by e-beam lithography: A novel active 2D photonic quasicrystal simulated, designed, fabricated and characterized

Quasiperiodic crystals (QCs) are a new class of materials that have fascinating optical properties lying somewhere between those of disordered and period structures. Advances in 2D photonic structures are expected in the introduction of active functionality into a 2D photonic QC. Semiconductor nanostructures are a very promising material as an active medium. CdSe/CdS core/shell nanorods (NR) present the appealing characteristics of strong and tunable light emission from green to red, are highly fluorescent and show linearly polarized emission. These characteristics open the way to a new class of hybrid devices based on polymers and colloidal NRs in which the unique optical properties of the inorganic moiety are combined with the processability of the host matrix to develop new high performing optical devices such as organic light-emitting diodes, ultra-low threshold lasers and non-linear devices. In this paper two-dimensional (2D) active new designed PQCs which consist of air rods in a nanocomposite prepa...

Bi2+2nO2+2nCu2−δSe2+n–δXδ (X = Cl, Br): A Three-Anion Homologous Series

Both layered multiple-anion compounds and homologous series are of interest for their electronic properties, including the ability to tune the properties by changing the nature or number of the layers. Here we expand, using both computational and experimental techniques, a recently reported three-anion material, Bi4O4Cu1.7Se2.7Cl0.3, to the homologous series Bi2+2 nO2+2 nCu2-δSe2+ n-δXδ (X = Cl, Br), composed of parent blocks that are well-studied thermoelectric materials. All of the materials show exceptionally low thermal conductivity (0.2 W/mK and lower) parallel to the axis of pressing of the pellets, as well as narrow band gaps (as low as 0.28 eV). Changing the number of layers affects the band gap, thermal conductivity, carrier type, and presence of a phase transition. Furthermore, the way in which the different numbers of layers are accessed, by tuning the compensating Cu vacancy concentration and halide substitution, represents a novel route to homologous series. This homologous series shows tunable properties, and the route explored here could be used to build new homologous series out of known structural blocks.