Cristian RADU

Lithium borohydride (LiBH4) is a promising hydrogen storage material releasing 13.8 wt% H2 upon decomposition in lithium hydride and boron, significantly surpassing other complex hydrides. However, sluggish dehydrogenation kinetics still hinder the use for practical applications. The infiltration of LiBH4 into carbon nanoscaffolds has proved to be effective in improving the hydrogen absorption/desorption (a/d) kinetics. Further improvement of storage kinetics can be achieved by modification of the nanocarbon with dopant elements. The present work compares nanoporous carbon (C-MSU-H) and C-MSU-H doped either with 1 at% N or 1 at% Ni as the matrix for infiltration of LiBH4. The catalytic effect of nitrogen proved to be superior to that of nickel (keeping the same doping level) for improving the hydrogen a/d kinetics of LiBH4 infiltrated in doped C-MSU-H. X-ray photoelectron spectroscopy was used to detect the amount and chemical proximity of nitrogen in nanoporous carbon following the thermal treatment in ammonia flow. The morphology and porosity of doped C-MSU-H were investigated by X-ray diffraction, FTIR, TEM, and BET. Hydrogen a/d kinetics of LiBH4@C-MSU-H nanocomposites was investigated by a volumetric method. The desorption peak temperatures (measured at 2 degrees C min-1 rate) are 339 degrees C for the undoped LiBH4@C-MSU-H, 328 degrees C for the LiBH4@C-MSU-H doped with 1 at% Ni and 318 degrees C for the LiBH4@C-MSU-H doped with 1 at% N nanocomposites. The activation energies of hydrogen desorption for the investigated nanocomposites were obtained from Kissinger plots: 142.7 kJ mol-1 for undoped LiBH4@C-MSU-H, 123.8 kJ mol-1 for LiBH4@C-MSU-H 1 at% Ni and 119.5 kJ mol-1 for LiBH4@C-MSU-H 1 at% N nanocomposites. The catalytic effect on LiBH4 dehydrogenation due to N-doping of nanocarbons is discussed.

This study explores how catalysts containing a low palladium loading (0.5 wt%) contribute to the selective hydrogenation of cinnamaldehyde. High specific surface area (SSA) mesoporous (2 wt%) TiO2 - SiO2 (UVM-7) materials were prepared by two different approaches: a one-step procedure, in which titania and silica precursors were added from the beginning to generate Ti2@UVM-7 support, and a two-step procedure, where TiO2 was deposited onto the UVM-7 silica surface via wet impregnation technique (Ti2/UVM-7). Both types of supports were decorated with Pd nanoparticles (NPs) through the deposition-precipitation technique. The obtained catalysts were thoroughly characterized by using different techniques, including XRD, N2 adsorption-desorption isotherms at liquid N2 temperature, ATR-FTIR, TEM-EDX, SEM-EDX, and XPS. Characterization data revealed that one-step procedure largely preserves the textural and structural properties of the support following the deposition-precipitation of the noble metal, whereas the two-step procedure slightly alters the UVM-7 morphology. Moreover, the preparation method of the supports impacts the Pd particle sizes and the metal-support interaction (MSI). The one-step procedure tends to promote the growth of larger Pd NPs, likely due to the TiO2 species being well embedded within the SiO2 matrix. In contrast, the two-step procedure yields well-dispersed Pd NPs smaller than 2 nm, due to the confinement of TiO2 nanodomains within the UVM-7 cavities, which enhances the MSI. Consequently, enhanced catalytic performance and stability were achieved with 0.5Pd/Ti2/UVM-7 (similar to 99% hydrocinnamaldehyde yield, TOF 4.81 s-1), due to the formation of very small Pd nanoparticles on the support that promote the MSI.

New approaches for the synthesis of magnetite (Fe3O4) nanoparticles (NPs) are of considerable interest due to their potential applications in various fields, such as biomedicine, industry, environmental remediation, and catalysis. This study presents a novel approach for synthesizing Fe3O4 NPs using high-energy electron beam (EB) irradiation starting from organic (acetylacetonates) iron precursors. EB irradiation is a challenging nanoparticle synthesis method, being at the same time efficient and rapid. The synthesis is carried out at room temperature and is based on the water radiolysis process. This eliminates the need for chemical-reducing agents and may provide precise control over particle formation. Using high-energy EB irradiation of an organic Fe precursor, we demonstrate the successful synthesis of well-dispersed Fe3O4 NPs with controlled size, morphology and magnetic properties, as proven by morpho-structural, M & ouml;ssbauer spectroscopy and magnetic investigations. In particular, using organic iron precursors, such as iron acetylacetonates, NPs with distinct surface characteristics and improved thermal stability compared to those synthesized from inorganic precursors were obtained. These findings suggest that integrating organic precursors in EB-assisted synthesis can enhance the functional properties of Fe3O4 NPs, making them more suitable for specific applications. The versatility of this method opens up new avenues for the targeted design of nanomaterials with specific functionalities, paving the way for advanced applications in various technological fields. The current study is also motivated by the lack of literature data on the synthesis of metallic iron or iron oxide NPs mediated by EB radiolysis.

Copper-zinc-tin-sulfide (Cu2ZnSnS4, CZTS) kesterites a promising earth-abundant and non-toxic absorber for next-generation thin-film photovoltaics. However, sulfur-based CZTS solar cells remain limited in performance, largely due to intrinsic defects and interfacial recombination losses. Here, we systematically investigate the impact of solvent chemistry and extrinsic doping and compositional engineering on the quality of solution-processed CZTS absorbers. A comparative study of three solvents, 2-methoxyethanol (MOE), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) reveals that all yield phase-pure, and compact films due to a robust Cu+-Sn4+ molecular precursor system, with MOE producing the most uniform morphology and superior optoelectronic properties. Rather than focusing on pure CZTS, the solvent screening is conducted on Cd-alloyed CZTS (CZCTS), as Cd incorporation substantially alters precursor coordination and crystallization behavior. Building on the optimized processing route, a synergistic compositional strategy combining silver (Ag) - cadmium (Cd) co-alloying with lithium (Li) doping is introduced to suppress cation disorder, passivate grain-boundary defects, and enhance carrier transport. As a result, the optimized he optimized absorber delivers a champion device with a power conversion efficiency of 10.6%, placing it among the highest efficiencies reported for solution-processed, selenium-free CZTS solar cells. These results highlight the critical role of solvent engineering coupled with targeted extrinsic doping in overcoming the long-standing limitations of CZTS photovoltaics and provide a scalable pathway toward environmentally benign thin-film solar technologies.

In situ exsolution has emerged as a powerful strategy for tailoring fuel electrode catalysts in solid oxide fuel cells (SOFCs), yet its integration with reversible exsolution-dissolution processes and its application to symmetricalcapable electrode design remain largely unexplored. Here, we demonstrate controlled exsolution-dissolution in nanofiber double perovskites as a rational route to engineer high-performance SOFC electrodes operable in both symmetrical and anode-supported configurations. Sm0.9Ba0.9Mn1.8-xFexCo0.1Ni0.1O5+delta nanofiber perovskites enable composition-dependent control of nanoparticle evolution. Under reducing conditions, socketed Co-Ni-Fe alloy nanocatalysts exsolve and partially embed into the perovskite lattice, while oxidation induces their transformation into Fe3-x-yNixCoyO4-type hollow core-shell nano-oxides via a Kirkendall-type mechanism. The nanofiber architecture promotes smaller and more densely distributed nanoparticles compared to powders, enhancing catalytic activity and redox stability. The optimized composite electrode delivers a low polarization resistance of 0.046 Omega cm2 at 800 degrees C. Anode-supported cells achieve a peak power density of 1112 mW cm-2 at 850 degrees C and 877 mW cm-2 at 800 degrees C, while symmetrical cells deliver 816 mW cm-2 at 800 degrees C with stable operation. This work establishes controlled exsolution-dissolution as a versatile platform for designing symmetrical-capable high-performance SOFC electrodes and highlights hollow core-shell nanostructure engineering as a powerful strategy for durable solid oxide electrochemical systems.

Polymorphism determines significant variations in materials' properties by lattice symmetry variation. If they are stacked together into multilayers, polymorphs may work as an alternative approach to the sequential deposition of layers with different chemical compositions. However, selective polymorph crystallization during conventional thin film synthesis is not trivial; changes of temperature or pressure when switching from one polymorph to another during synthesis may cause degradation of the structural quality. The present work reports on the single-step ion-beam-assisted fabrication of multilayered polymorph structures while applying the disorder-induced ordering approach. The dynamic annealing of disorder may be tuned, during ion irradiation, toward self-assembling of several polymorph interfaces. Gallium oxide multilayers with two polymorph interface repetitions are obtained. The single-crystal structure of the polymorphs is maintained between interfaces, exhibiting repeatable crystallographic relationships and optical properties. These data pave the way for enhancing materials' functionalities using not previously conceived capabilities of ion beam technology.

We theoretically study the 2D Su-Schrieffer-Heeger model in the context of Floquet topological insulators (FTIs). FTIs are systems which undergo topological phase transitions, governed by Chern numbers, as a result of time reversal symmetry (TRS) breaking by a time periodic process. In our proposed model, the condition of TRS breaking is achieved by circularly polarized light irradiation. We analytically show that TRS breaking is forbidden in the absence of second order neighbors hopping. In the absence of light irradiation, we identify a symmetry-protected degeneracy and prove the appearance of a flat band along a specific direction in the momentum space. Furthermore, we employ a novel method to show that the four unit cell atoms, in the absence of irradiation, can be interpreted as conserved spin states. With the breaking of TRS via light irradiation, these spin states are no longer conserved, leading to the emergence of chiral edge states. We also show how the interplay between the TRS breaking and dimerization leads to some complex topological phase transitions. The validity of our findings is substantiated through Chern numbers, spectral properties, localization of chiral edge states and simulations of quantum Hall transport. Our model is suitable not only for condensed matter (materials), but also for cold gases trapped in optical lattices or topolectrical circuits.

We report on the increase of luminescence of ZnS:Ag after exposure to a radio-frequency (RF) argon plasma at low powers ranging from 5W to 50W. The best luminescence enhancement was achieved at 5W RF power, when the increase was approximately 57.02 % over a 35-min exposure. The luminescence is measured in-situ by excitation with an electron beam with energy 13 keV and a fiber coupled to a spectrometer. The increase in luminescence is attributed to the cleaning effect of surface defects of the crystal caused by argon ions accelerated in the plasma sheath. Surface impurities were highlighted by TEM and XPS analysis. Zn2p(3/2), Zn2p(1/2) and S2p(3/2) peaks show initially high oxidation state and after plasma treatment they shifted to lower value which indicated a decontamination of trapped oxygen. At higher RF powers up to 50W, the trend of increased luminescence continues, but it is mitigated by the thermal quenching effect and sulfur depletion observed in EDS analysis. Calculations based on power deposition indicate a thermoquenching point of approximately 130-150 degrees C.

Pnictogen chalcohalide semiconductors are emerging materials with broad potential in energy-related applications, including solar cells, photocatalysis, photodetectors, batteries, supercapacitors, thermoelectric and piezoelectric generators. Their compositional flexibility allows fine tuning of structural and optoelectronic properties. In this study, microcrystalline powders of Sb1-xBixSeI (x = 0-1) were synthesized from binary precursors by a solid-state method in evacuated quartz ampoules. Energy dispersive spectroscopy confirmed the successful substitution of Sb with Bi in Sb1-xBixSeI. The formation of solid solutions was also supported by Raman spectroscopy and X-ray diffraction (XRD). All materials exhibited needle-shaped crystal morphologies and orthorhombic crystal structure (Pnma), regardless of the Bi/Sb ratio. XRD patterns shifted toward smaller angles with increasing Bi content, indicating lattice expansion. Calculated lattice parameters (b and c) increased linearly with Bi incorporation, while the lattice parameter (a) remained constant. Raman spectra exhibited characteristic peaks at 182 cm- 1 for Bi-Se vibration and 209 cm- 1 for Sb-Se vibration, with intensity ratios reflecting Bi content. UV-Vis-NIR diffuse reflectance spectroscopy revealed a direct band gap that decreased from 1.7 eV (SbSeI) to 1.29 eV (BiSeI). Room-temperature photoluminescence measurements exhibited a single emission band, shifting from 1.75 eV to 1.41 eV with increasing Bi content. Ultraviolet photoelectron spectroscopy indicated a shift in the valence band maximum from 0.44 eV (SbSeI) to 1.1 eV (BiSeI). These findings highlight the tunability of Sb1-xBixSeI compounds, offering pathways for optimizing their properties for specific optoelectronic applications.

The present research explores for the first time the intricate relationship between sulfurization temperature at unusual high temperatures (up to 700 degrees C) and the structural/optoelectronic properties of Cu-2(Zn,Cd)SnS4 (CZCTS) thin films, synthesized via a two-step sequential process involving the precursor film deposition using aprotic molecular ink followed by thermal treatment in sulfur atmosphere. X-ray diffraction patterns confirms the tetragonal structure. Scanning Electron Micrographs revealed significant grain growth, with grain sizes increasing from similar to 0.3 mu m at 620 degrees C to similar to 1.5 mu m at 680 degrees C, effectively reducing grain boundary recombination. Energy dispersive X-ray spectroscopy demonstrated a Cu-poor and Zn-rich composition, with a consistent Cd incorporation of similar to 3.7 at%. Raman spectroscopy showcases the homogeneity and purity of the CZCTS crystalline structure. Precise control of the sulfurization temperature plays a crucial role in determining the photovoltaic characteristics of CZCTS-based solar cells. By increasing the grain size and preventing the thermal decomposition of the CZTS phase, the photovoltaic performance peaked at a sulfurization temperature of 680 degrees C, achieving a power conversion efficiency (PCE) of 10.4%, with an open-circuit voltage of 0.701 V, a short-circuit current density of 24.3 mA/cm(2) and a fill factor of 60.8%. External quantum efficiency reached a maximum of 83.3% at 580 nm. The bandgap of the CZCTS absorber was determined to be 1.48 eV, optimal for photovoltaic applications. However, further increasing the sulfurization temperature to 700 degrees C resulted in a lower PCE of 8.5%, attributed to interface degradation and secondary phase formation. Temperature-dependent current-voltage measurements revealed a reduction in recombination losses, with an activation energy of 1.24 eV at the CZCTS/CdS interface, indicating effective defect passivation by Cd incorporation. The optimized films, sulfurized at 680 degrees C, displayed an absorber thickness of similar to 1.2 mu m after sulfurization, providing efficient light absorption and charge transport. The findings not only emphasize the critical role of sulfurization temperature in engineering CZCTS film and subsequently their functionality but also provide valuable insights for fine tuning their performance in the field of photovoltaic applications.

We investigate the second-order Floquet topological (SOFT) phase transitions, from the perspective of spatial symmetries. In this respect, we consider a generic honeycomb lattice Floquet topological insulator (FTI), realized by circularly polarized light irradiation, in the presence of spin-orbit coupling (Kane-Mele model). We find that our studied FTI presents chiral symmetry on a preferential direction in Fourier space, the same property that protects the topological phases in the Su-Schrieffer-Heeger (SSH) model. Thus we were allowed to characterize the SOFT phases in terms of mirror-graded winding numbers (Zak phase). Moreover, our model exhibits C2 and C3 symmetry in Fourier space, a property which lead us to investigate two finite structures having the aforementioned symmetries, namely, rhombic and triangular shapes. Indeed, we find that both of them undergo SOFT phase transitions, characterized by the appearance of 0D corner states symmetrically localized over the whole sheet. Finally, we investigate the C2 and C3 symmetry breaking. Interestingly, we reveal that the corner states are not destroyed, but localize at preferential corners instead, giving rise to a corner polarization.

Despite the promise of high-k dielectrics, inherent limitations persist in transistor scaling and enhancing energy efficiency, including a fundamental threshold of 60 mV/dec for increasing drain current by an order of magnitude. Proposed solutions involve negative capacitance at the gate oxide to overcome this barrier using ferroelectric structures. Efforts to understand and regulate the switching dynamics and intricate electrostatic configurations of ferroelectric structures towards achieving negative capacitance regimes have intensified. While standalone ferroelectric capacitors cannot stabilize negative capacitance without external fields, multilayered thin films offer a promising solution. Typically, ferroelectric layers are paired with dielectrics/insulator, demonstrating steady-state negative capacitance, often at nanoscale or specific temperature domains. This study aims to stabilize negative capacitance in ferroelectric structures by inducing internal electric fields, aligning the system near coercivity, particularly in bilayer structures formed by two ferroelectric layers with slight differences in polarization values, such as p-n heterojunctions using Pb (Zr,Ti)O3 PZT) with different doping as Fe, Nb, Bi. Most of these structures exhibit evident amplification of capacitance compared to the equivalent series-connected capacitance, across a large temperature domain. The complex capacitance-frequency characteristic of these structures indicates a complex equivalent circuit. Analysis of these complex circuits compared with simple component layers concludes that at least one of the FE layers in these bilayer structures is in a negative capacitance (NC) state.

Cerium dioxide (CeO2) thin films with pyramidal nanostructures exhibiting a fractal aspect are suitable for various applications that require a large surface area. An accurate model of these films is valuable not only for optimizing the properties for specific applications but also for predicting and understanding the growth mechanism. In this paper, we present the foundation of a simulation for the growth of CeO2-x nanostructured thin films. We propose a 3-dimensional model of the surface nanostructures and link the morphology with crystallographic orientations and growth modes. To validate our model, we fabricated CeO2_ x thin films with different thicknesses using pulsed laser deposition (PLD) and characterized their morphological and structural properties. The evolution of our films shows the representative features of the Stranski-Krastanov model. The morphology changes from compact and smooth to dendritic with pyramidal nanostructures. The texture of our film also changes with thickness, and the preferential orientations are (111) and (220). Additionally, we characterize the CeO2_ x thin films from the chemical and optical points of view. The stoichiometry of CeO2 is not fully achieved, our thin films present the Ce3+ oxidation state at the surface. The formation of C-type Ce2O3 with fluorite structure can be associated with a small refractive index and small band gap.

Floquet topological insulators (FTIs) are materials which undergo topological phase transitions under a time periodic perturbation causing time reversal symmetry breaking. In this Letter, we propose a spin filter model based on a FTI realized by irradiating a honeycomb lattice with circularly polarized light, in the presence of intrinsic spin-orbit coupling. The main ingredient of our proposed mechanism of Floquet topological spin filter (FTSF) implementation is the presence of an on-site staggered potential which controls independently the topological phases of the two existent spin states. After giving a numerical example of the occurrence of the FTSF phase, we argue that the origin of the FTSF phase resides in the spatial inversion symmetry breaking due to the presence of a staggered potential. The light helicity degree of freedom may be used to select the filtered spin state. Moreover, due to the topological properties of our model, the spin will be purely filtered in a Hall transport experiment. We discuss also the experimental feasibility.

In a milestone paper [F. D. M. Haldane, Phys. Rev. Lett. 61, 2015 (1988)], Haldane elaborated a model of graphene within the time -reversal symmetry breaking is achieved by next -nearest -neighbors imaginary counterrotating hopping, hence conferring topological properties. In recent years, the time -reversal symmetry turned out to be broken also by light irradiation in so-called Floquet topological insulators (FTIs). On the other hand, Kane and Mele introduced a spin -orbit coupling (SOC) model [C. L. Kane et al., Phys. Rev. Lett. 95, 226801 (2005)] inspired by the Haldane's mechanism. In this paper, we present the topological properties of a FTI possessing SOC, using graphene as the playground. It was found that the interplay between sublattice subspace and the spin one triggers interesting topological phase transitions. Basically, in a FTI with SOC, two topological phases may be excited: charge quantum Hall effect (CQHE) and, respectively, spin quantum Hall effect (SQHE) phases. Also, it was demonstrated that the CQHE and SQHE coexistence is forbidden by the topology of the system. As well, it was identified a special driving regime of spin filter (SF), in which only one spin state is topological and, consequently, will be filtered in quantum transport.

Rare-earth doped GdF3 nanocrystals embedded in silica glassy matrix have been prepared by controlled crystallization of the xerogel; the influence of rare-earth ion (Pr, Sm, Eu, Tb, Dy, Er, Yb) and additional Li-codopant on structural and optical properties was discussed. The precipitation of RE-doped GdF3 nanocrystalline phase is the result of Gd-trifluoracetate thermolysis revealed as a strong exothermic peak at around 300 degrees C. Structural analysis of RE-doped SiO2-GdF3 glass-ceramic sample calcined at 525 degrees C showed the occurrence of GdF3 nanocrystals of about 25 nm size, showing hexagonal or orthorombic structure depending on the RE-ion. Under UV-light excitation at 273 nm of Gd3+ ions (S-8(7/2) -> I-6(13/2,15/2) transition), photoluminescence spectra showed characteristic RE3+ luminescence due to the non-radiative energy transfer between the excited Gd3+ and acceptor RE ions; the highest energy transfer (congruent to 80 %) was observed for Tb3+ and lowest (congruent to 21 %) for Sm3+.

Magneto-optical measurements enable the identification of Fe2+ and Fe3+ in the R and S blocks of BaFe12O19 Mhexaferrite powder obtained by sol -gel processing, followed by thermal annealing at 900 C for 3 hours. The ferromagnetic phase is evidenced by the spin-majority configuration (Fe3+) due to their unpaired electrons between d -d orbitals, while the Fe2+ in the low spin possesses diamagnetic behavior strongly dependent on the surrounded crystal field. Additionally, the irradiation with gamma rays changes the ratio between Fe2+/Fe3+, mainly on the surface of BaFe12O19 nanocrystals. These changes were confirmed by X-ray Photoelectron Spectroscopy measurements, in which the concentration of Fe2+ increased from 69% to 82%, while the one of Fe3+ decreased from 31% to 18%. he thermoluminescent measurements reveal the same changes of Fe3+ in Fe2+ by electron capturing during irradiation, which is released as a red emission after recombination processes. The changes are explained by the increasing of some Fe-O bonds along the c-axis, mainly due to breaking a part of these bonds. The X-ray analysis confirms the changing of the parameters for the BaFe12O19 hexagonal structure.

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.

Featuring a high hydrogen storage content of up to 20 wt%, complex metal borohydrides remain promising solid state hydrogen storage materials, with the real prospect of reversible behavior for a zero-emission economy. However, the thermodynamic barriers and sluggish kinetics are still barriers to overcome. In this context, nanoconfinement has provided a reliable method to improve the behavior of hydrogen storage materials. The present work describes the thermodynamic and kinetic enhancements of LiBH4 nanoconfined in MFe2O4 (M=Co, Ni) ferrite-catalyzed graphene host. Composites of LiBH4-catalysts were prepared by melt infiltration and investigated by X-ray diffraction, TEM, STEM-EDS and TPD. The role of ferrite additives, metal precursor treatment (Ar, Ar/H-2) and the effect on hydrogen storage parameters are discussed. The thermodynamic parameters for the most promising composite LiBH4-graphene-NiFe2O4 (Ar) were investigated by Kissinger plot method, revealing an E-A = 127 kJ/mol, significantly lower than that of neat LiBH4 (170 kJ/mol). The reversible H-2 content of LiBH4-graphene-NiFe2O4 (Ar) after 5 a/d cycles was similar to 6.14 wt%, in line with DOE's target of 5.5 wt% storage capacity, while exhibiting the lowest desorption temperature peak of 349 degrees C. The composites with catalysts treated in Ar have lower desorption temperature due to better catalyst dispersion than using H-2/Ar.

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.

A multi-step ion-exchange methodology was developed for the fabrication of Cu(LaTa2O7)(2) lamellar architectures capable of wastewater depollution. The (001) diffraction line of RbLaTa2O7 depended on the guest species hosted by the starting material. SEM and TEM images confirmed the well-preserved lamellar structure for all intercalated layered perovskites. The UV-Vis, XPS, and photocurrent spectroscopies proved that Cu intercalation induces a red-shift band gap compared to the perovskite host. Moreover, the UV-Vis spectroscopy elucidated the copper ions environment in the Cu-modified layered perovskites. H-2-TPR results confirmed that Cu species located on the surface are reduced at a lower temperature while those from the interlayer occur at higher temperature ranges. The photocatalytic degradation of phenol under simulated solar irradiation was used as a model reaction to assess the performances of the studied catalysts. Increased photocatalytic activity was observed for Cu-modified layered perovskites compared to RbLaTa2O7 pristine. This behavior resulted from the efficient separation of photogenerated charge carriers and light absorption induced by copper spacer insertion.

AuxFe1-x nanophase thin films of different compositions and thicknesses were prepared by co-deposition magnetron sputtering. Complex morpho-structural and magnetic investigations of the films were performed by X-ray Diffraction, cross-section Transmission Electron Microscopy, Selected Area Electron Diffraction, Magneto Optical Kerr Effect, Superconducting Quantum Interference Device magnetometry and Conversion Electron Mossbauer Spectroscopy. It was proven that depending on the preparation conditions, different configurations of defect alpha-Fe magnetic clusters, i.e., randomly distributed or auto-assembled in lamellar or filiform configurations, can be formed in the Au matrix. A close relationship between the Fe clustering process and the type of the crystalline structure of the Au matrix was underlined, with the stabilization of a hexagonal phase at a composition close to 70 at. % of Au and at optimal thickness. Due to different types of inter-cluster magnetic interactions and spin anisotropies, different types of magnetic order from 2D Ising type to 3D Heisenberg type, as well as superparamagnetic behavior of non-interacting Fe clusters of similar average size, were evidenced.

Luminescent nanocrystals embedded into silica microspheres were shown to be useful for silica labeling for biological applications, ensuring mechanical and chemical stability, nontoxicity, biocompatibility and optical properties. We used sol-gel technology to prepare silica nanospheres embedded with fluorescent and magnetic Eu3+(1 mol%)-doped CeO2 nanocrystals. The X-ray diffraction pattern analysis and transmission electron microscopy investigations showed CeO2:Eu3+(1 mol%) nanocrystals of about 9 nm size and Ce3+ ions substitution by the Eu3+ ions; the nanocrystals dispersed inside the nanosized silica spheres of about 400 nm diameters. The photoluminescence spectra recorded under UV-light excitation showed Eu3+ ions luminescence peaks (D-5(0)-F-7(J), J = 0-4) accompanied by a weaker 425 nm luminescence due to the silica matrix; the quantum yield was 0.14. The weak hysteresis loop and magnetization curves recorded up to 20,000 Oe showed dominantly paramagnetic behavior associated with the silica matrix; a slight opening of the hysteresis loop to a very small magnetic field (about 0.005 Oe) was due to the presence of the two rare earth ions. The photonic crystal properties of SiO2-CeO2:Eu3+(1 mol%) silica nanospheres deposited as films on quartz plates were revealed by the two weak attenuation peaks at 420 and 500 nm and were associated with the reflection from different planes. The SiO2-CeO2:Eu3+(1 mol%) nanospheres are attractive potential candidates for photonics-related applications or for multifunctional bio-labels by combining the luminescence and magnetic properties of the nanocrystals.

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.

A new methodology to obtain magnetic information on magnetic nanoparticle (MNP) systems via electron tomography techniques is reported in this work. The new methodology is implemented in an under-development software package called Magn3t, written in Python and C++. A novel image-filtering technique that reduces the highly undesired diffraction effects in the tomography tiltseries has been also developed in order to increase the reliability of the correlations between morphology and magnetism. Using the Magn3t software, the magnetic shape anisotropy magnitude and direction of magnetite nanoparticles has been extracted for the first time directly from transmission electron tomography.

This contribution concerns the effect of the chemical composition of the brucite-type layer of bi-cationic LDH materials ZnxAl and MgxAl (x = 2-5) and tri-cationic LDH MgyZnzAl (y + z = 4, y = 1, 2, 3) on their catalytic activity for olefin epoxidation with H2O2 in the presence of acetonitrile. LDH materials were prepared by the standard method of co-precipitation at constant pH 10, using an aqueous solution of the corresponding metal nitrates and a basic solution containing NaOH and Na2CO3. The fresh LDHs were calcined to yield the corresponding mixed oxides and then the recovery of the LDH structure by hydration of the mixed oxides was performed. The resulting samples were characterized by AAS, XRD, DRIFT, DR-UV-Vis, BET and determination of basic sites. The results of the catalytic tests for olefin epoxidation were well correlated with the basicity of the samples, which was in turn related to the M2+/Al3+ ratio and the electronegativity of different bivalent metals in the brucite-type layer.

Anode modification with carbon nanomaterials is an important strategy for the improvement of microbial fuel cell (MFC) performance. The presence of nitrogen in the carbon network, introduced as active nitrogen functional groups, is considered beneficial for anode modification. In this aim, nitrogen-containing carbon nanostructures (NCNs) with different morphologies were obtained via carbonization of polyaniline and were further investigated as anode modifiers in MFCs. The present study investigates the influence of NCN morphology on the changes in the anodic microbial community and MFC performance. Results show that the nanofibrillar morphology of NCNs is beneficial for the improvement of MFC performance, with a maximum power density of 40.4 mW/m(2), 1.25 times higher than the anode modified with carbonized polyaniline with granular morphology and 2.15 times higher than MFC using the carbon cloth-anode. The nanofibrillar morphology, due to the well-defined individual nanofibers separated by microgaps and micropores and a better organization of the carbon network, leads to a larger specific surface area and higher conductivity, which can allow more efficient substrate transport and better bacterial colonization with greater relative abundances of Geobacter and Thermoanaerobacter, justifying the improvement of MFC performance.

Polarization switching in ferroelectric films is exploited in many applications, such as non-volatile memories and negative capacitance field affect transistors. This can be inhomogeneous or homogeneous, depending on if ferroelectric domains are forming or not during the switching process. The relation between the polarization switching, the structural quality of the films and the negative capacitance was not studied in depth. Here, Pb(Zr0.2Ti0.8)O-3 (PZT) layers were deposited by pulse laser deposition (PLD) and sol-gel (SG) on single crystal SrTiO3 (STO) and Si substrates, respectively. The structural quality was analyzed by X-ray diffraction and transmission electron microscopy, while the electric properties were investigated by performing hysteresis, dynamic dielectric measurements, and piezo-electric force microscopy analysis. It was found that the PZT layers grown by PLD on SRO/STO substrates are epitaxial while the layers deposited by SG on Pt/Si are polycrystalline. The polarization value decreases as the structure changes from epitaxial to polycrystalline, as well as the magnitude of the leakage current and of the differential negative capacitance, while the switching changes from homogeneous to inhomogeneous. The results are explained by the compensation rate of the depolarization field during the switching process, which is much faster in epitaxial films than in polycrystalline ones.

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Indium-doped tin oxide (ITO) thin films were fabricated by radio frequency magnetron sputtering and were subjected to in-situ and ex-situ annealing, at 200 degrees C, 300 degrees C and 400 degrees C, respectively. The in-situ thermal treatment consisted to intentionally heating the samples' substrates, while the ex-situ annealing was performed using an oven, under ambient atmosphere. For the ITO samples subjected to ex-situ annealing, the density of oxygen vacancies increased leading to the decrease of the electrical resistivity. No significant changes were noticed in terms of transmission spectroscopy after the thermal treatment; while by evaluating the Skewness parameter was determined that the annealing improves the planarity of samples' surface.

The present work proposes the simultaneous removal of these classes of pollutants by a catalytic hydrotreatment processes. For this purpose, bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu of 4:1) supported on macroporous strong base anion resin were prepared by different methods. The catalysts were characterized (by XRD, SEMEDX, XPS, AAS and H-2 chemisorption) and tested in a continuous flow system. The selected catalyst preparation protocol consists in a two-step method, which implies the deposition of palladium by ion exchange and the subsequent deposition of copper by controlled reaction on the surface of the pre-reduced palladium. The effectiveness of the catalyst in the simultaneous reduction of nitrate and hydrodechlorination of 4-chlorophenol was demonstrated. By adjusting the initial pH and the flow rate of the aqueous solution, nearly complete hydrodechlorination of 4-chlorophenol can occur together with selective nitrate reduction at a conversion of 95% and a selectivity to N-2 of 92% (this value contains the contribution of all gaseous products, including the eventually formed NOx). The bimetallic catalyst was found to remains relatively stable after 100 h of test time.

Water splitting by means of semiconducting photoelectrodes and solar light represents a promising alternative to conventional fossil fuel economy. In this process the photoactive electrode absorb sunlight directly thus initiating the photochemical reaction which create excess electrons in the conduction band of the semiconducting electrode. Titanium doped iron oxide seems to be a promising semiconducting material for photoelectrodes. Consequently, we investigated the effect of Ti doping on the structure, electrical and photoelectrochemical properties alpha-Fe2O3. The Ti doped alpha-Fe2O3 were prepared by a slightly modified mixed oxide route, consisting in a prolonged mixing of the raw materials in a high energy planetary ball mill until the particles decreased to the nanometric sizes. Optimum results were obtained for samples doped with 5 at. % titanium and sintered at 1200 degrees C. Photocurrents as high as 8.4 mA/cm(2), for illumination from a 300 W xenon lamp, were recorded for such samples. It is hoped that such photoelectrodes show promise for water splitting.

PdCu nanoparticles were synthesized by the alkaline polyol method and further supported on alumina or titania. The nanoparticles show a crystalline Pd core and a shell rich in amorphous copper as was put in evidence by complex characterization methods (X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and CO chemisorption). The performances of as-prepared catalysts in the water phase reduction of nitrate were assessed in comparison with catalysts obtained by impregnation. Supported nanoparticle catalysts show a high activity in the reduction of nitrates, better than the impregnated catalysts. The importance of the support choice was discussed. The catalyst based on PdCu nanoparticles supported on titania (PCT-np) is the most active, selective, and stable among those investigated. Also, the influence of pH conditions on the PCT-np catalyst performances was emphasized.

Large-scale microstructures were imprinted on the surface of silicon with dimensions of 1 mm x 1 mm by femtosecond laser line-by-line scanning irradiation. The scanning was made under air and under chlor/hydrogen based liquid layers. Scanning electron microscope investigations evidenced homogeneous surface microstructures, such as: ripples with sub-wavelengths dimensions, Si pillars and directional oriented bacilliform structures. The dependence of the surface morphology on laser energy, scanning speed and irradiation media was analyzed. In air, the microstructure changes from directional-arranged bacilliform structures to well-known ripple structures with a width of about 525 nm. When using the liquid media, we observe ripple structures with a width of about 370 nm and an overlapping of those that evolve in certain regions into Si pillars. The surfaces show interesting gradient topography behaviour which could be used as model scaffolds for the systematic exploration of the role of 3D micro/nano morphology on cell adhesion and growth. By using chlor and hydrogen based liquids we were able to explore the microstructuring of the silicon by line-by-line irradiation process using the femtosecond laser. (C) 2011 Elsevier B. V. All rights reserved.

The purpose of this work was to obtain precipitated calcium carbonate (PCC) particles in polymorphic form of vaterite via gas-liquid route in controlled pH conditions. The effect of CO2 concentration (12.5-100%), feed gas (CO2-air) flow rate, pH, and conductivity of solution upon the PCC particles properties was studied. On the basis of the experimental data, the main factors leading to vaterite formation as major product were established. It was found that the buffer solution has a decisive role in determining polymorphic phase of PCC while CO2 concentration and feed gas flow rate have no significant influence. It was demonstrated that spherical vaterite particles of high purity can be produced under controlled reaction conditions. Also, some considerations on the mechanism of carbonation process were formulated.

The aim of this study is to investigate the micrometer and submicrometer scale structuring of silicon by liquid chlorine and fluorine precursors with 200 fs laser pulses working at both fundamental (775 nm) and frequency doubled (387 nm) wavelengths. The silicon surface was irradiated at normal incidence by immersing the Si (111) substrates in a glass container filled with liquid chlorine (CCl(4)) and fluorine (C(2)Cl(3)F(3)) precursors. We report that silicon surfaces develop an array of spikes with single step irradiation processes at 775 nm and equally at 387 nm. When irradiating the Si surface with 400 pulses at 330 mJ/cm(2) laser fluence and a 775 nm wavelength, the average height of the formed Si spikes in the case of fluorine precursors is 4.2 mu m, with a full width at half maximum of 890 nm. At the same irradiation wavelength chlorine precursors develop Si spikes 4 mu m in height and with a full width at half maximum of 2.3 mu m with irradiation of 700 pulses at 560 mJ/cm(2) laser fluence. Well ordered areas of submicrometer spikes with an average height of about 500 nm and a width of 300 nm have been created by irradiation at 387 nm by chlorine precursors, whereas the fluorine precursors fabricate spikes with an average height of 700 nm and a width of about 200 nm. Atomic force microscopy and scanning electron microscopy of the surface show that the formation of the micrometer and sub-micrometer spikes involves a combination of capillary waves on the molten silicon surface and laser-induced etching of silicon, at both 775 nm and 387 nm wavelength irradiation. The energy-dispersive x-ray measurements indicate the presence of chlorine and fluorine precursors on the structured surface. The fluorine precursors create a more ordered area of Si spikes at both micrometer and sub-micrometer scales. The potential use of patterned Si substrates with gradient topography as model scaffolds for the systematic exploration of the role of 3D micro/nano morphology on cell adhesion and growth is envisaged. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3619856]

CuO/Al2O3 and NiO/Al2O3 catalysts prepared by incipient wetness impregnation were used for the oxidation of Reactive Black 5 (RB5) in aqueous solution. Removal of the dye was assessed by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) measurements and the generation of the hydroxyl radicals in the process was evaluated by chemiluminescence measurements. To put in evidence the interaction RB5 - catalyst and the surface species formed onto catalysts during the oxidation, Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis was performed. A different behavior of the two catalytic systems was revealed by the comparative analysis of the data obtained from the adsorption and oxidation tests. Only CuO/Al2O3 was effective in the RB5 degradation, NiO/Al2O3 acted as a simple adsorbent. In the presence of CuO/Al2O3, at H2O2 concentration of 40 mM the azo dye was totally eliminated from both solution and catalyst surface after 4 h, with a mineralization degree higher than 90%. However, a strong inhibition of the catalytic oxidation of RB5 was observed in the presence of phosphate ions. In the conditions of hydrogen peroxide excess, the rate equation in the case of copper catalyst was simply expressed by a pseudo-first order equation and the model was found to fit well the data. The amount of copper leached from catalyst during the oxidation process was only 1.0-1.6% per cycle leading to the conclusion that the decrease of the dye mineralization with the number of cycles has to be explained mostly by the surface covering with the reaction products, at least to a certain extent. (C) 2010 Elsevier B.V. All rights reserved.

Preparation of modified ruthenium molecular sieves has been investigated in two steps deposition of ruthenium and modifying of ruthenium molecular sieves in presence of ligands. As support sieve there were used two molecular sieves with large pore apertures and low acidity strength (zeolite L and APO-34). Correlation of in situ W-VIS ruthenium deposition measurements with catalyst characterisation revealed that ruthenium deposition takes place not only through ionic exchange but also through adsorption of ruthenium hydrolysed species. Modifying of the ruthenium molecular sieves catalysts with ligands has as effect a diminution of electronic charge on metal. The experimental data indicate that the presence of ligand favours an enantioselective hydrogenation of D-fructose to D-mannitol even if the yields are not very high.