Publications

Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.

Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti3C2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti3C2, hydroamination exhibits almost complete selectivity for the anti-Markovnikov regioisomer, for both aliphatic amines and less-reactive aromatic amines. Ti3C2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C-C multiple bonds is a reaction with complete atom efficiency that may form C-N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti3C2 nanosheets is quantified by thermoprogrammed NH3 desorption. The measured TOF values are on the order of 102 h-1, with the highest TOF value being 350 h-1 for 1-hexyne hydroamination by n -butylamine. Therefore, Ti3C2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.

Herein we present a comparative study among different spray-coated nanometric mesoporous electron transporting layers (ETLs) in perovskite solar cells (PSC), namely m-TiO2, 2 , m-SnO2 2 and m-SnO2 2 quantum dots (mSnO2QDs). 2 QDs). The solutions used for deposition were prepared from commercial pastes and colloidal suspensions for m-TiO2 2 and m-SnO2. 2 . For m-SnO2QDs 2 QDs in-house QDs solutions were prepared. The formamidiniummethylamonium-potassium (FAMA@10 K) has been used as light absorber material in the fabricated PSCs. The structural, compositional and morphological studies, correlated with the photovoltaic performance of PSCs, indicate that the m-SnO2 2 QDs layer is the best candidate among the three investigated mesoporous ETLs. Compared with the suspensions used for the other two ETLs, the in-house prepared SnO2 2 QDs solution presents smaller agglomerates of nanoparticles and results in the formation of a thinner, more uniform and compact mesoporous ETL. The FAMA@10 K perovskite deposited on m-SnO2 2 QDs ETL presents a lower roughness, better uniformity and a higher amount of PbI2. 2 . Our work unveils that the SnO2 2 QDs solution can be easily produced in laboratory and when is deposited as mesoporous scaffold in a PSC with FAMA@10 K perovskite, the power conversion efficiency increases up to 14.90 %, being with up to 27 % larger than in the PSCs with m-TiO2 2 and mSnO2 2 ETLs prepared from commercial solutions. By modeling the J-V dynamic hysteresis with more than 90 % match between the calculated and experimental J-V data, for all three types of mesoporous ETLs, the relevant parameters that explain the hysteresis magnitude and account for ionic-induced recombination processes in PSCs were determined.

Tungsten-copper (W-Cu) composites have a wide range of engineering applications, from arc-resistant electrodes and high-voltage electrical contacts to heat sinks for integrated circuits and plasma-facing components for fusion reactors. They combine high corrosion and erosion resistance, very good thermal and electrical conductivity, low thermal expansion, with good mechanical properties. However, the fabrication of such materials is limited in terms of shape complexity and the internal distribution of the individual phases. Furthermore, the dissimilar thermo-mechanical properties (melting temperature, thermal conductivity, coefficient of thermal expansion) of the constituent phases impose severe constraints on the fabrication and use of W-Cu composites. To overcome the challenges of component design and enable greater freedom in terms of composition, W-Cu composites were produced by a combination of additive manufacturing and liquid-melt infiltration (LMI). Porous W-lattice structures were manufactured by laser powder-bed fusion (LPBF) followed by infiltration with molten Cu. A series of composites was produced with Cu contents from 3 to 75 vol% and evaluated in terms of thermal, electrical, and mechanical properties. The LPBF-LMI W-Cu composites exhibited comparable thermo-mechanical properties to W-Cu materials manufactured using powder-metallurgical processing, but with an expanded composition range and shape complexity. Lower thermal expansion coefficients (4.5-5.8 x 10-6 K- 1) and an improved thermal stability of the Young's modulus, only a 27-33 GPa decline in the range 27-827 degrees C, were observed for all the compositions, which was ascribed to the W-phase connectivity in all the W-Cu composites, independent of the volume fraction of Cu.

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 show in theory and experiment that in periodically patterned spintronic terahertz emitters (STEs), charge dynamics can modify the emission spectrum in a well-controlled way. Characterization of nanopatterned STEs at frequencies up to 30 THz shows that the STE emission spectrum systematically changes with emitter size. The spectral intensity exhibits significant reductions at frequencies below 4 THz, accompanied by pronounced dips at around 15 and 24 THz. While reduction of the STE size enhances the modulation of all features, it does not alter the dip frequencies. The effect originates from the charging of the structure's edges by terahertz currents, causing a backflow that interferes with the initially induced current pulse. An analytical model quantitatively reproduces these results and agrees well with the findings of control experiments. Our findings enable a detailed investigation of the charge dynamics in STEs and provide additional means for controlled shaping of STE emission spectra by nanopatterning.

This study investigates the fabrication of short-wavelength infrared (SWIR) photosensitive amorphous and nanocrystalline Ge1-xSnx:H thin films by magnetron sputtering from separate Ge and Sn targets using different Ar: H mixing ratios as working gas. Amorphous Ge1-xSnx:H films have been obtained on both c-Si and fused quartz substrates at ambient temperature, while dynamic nanocrystallization occurs in-situ when the substrate temperature during deposition is raised to 200 degrees C. Fourier-transform infrared spectroscopy has shown the hydrogen incorporation by detecting an absorption line at 1873 cm(-1), close to the value corresponding to Ge-H bonding, only in the room temperature amorphous films. Based on that, we infer that the hydrogen concentration is very low in the films deposited at high temperature. The higher concentration of hydrogen in the amorphous samples is associated with an increase of the absorption gap to 0.5 eV compared to 0.3 eV in the 200 degrees C samples. In-situ (during deposition) and ex-situ (by subsequent rapid thermal annealing) nanocrystallization have been analyzed by high-resolution transmission electron microscopy, X-ray diffraction and micro-Raman spectroscopy. SWIR spectral photosensitivity up to 2.4 mu m was found to be more than two orders of magnitude improved in hydrogenated amorphous films with high hydrogen content, compared to the nanocrystalline ones that are weakly hydrogenated. These findings demonstrate the potential of hydrogenation to enhance the photoelectric properties of GeSn sputtering films for optoelectronic SWIR infrared applications.

Herein we show that the Ti3SiC2 MAX phase can be used as a support for deposition of different amounts of metal oxides (MOx, M = Cu or V) (5, 10 and 20 wt%) for the direct oxidation of methane to formaldehyde using molecular oxygen, at relatively low temperatures and atmospheric pressure. The oxides were deposited using a hydrothermal method at 180 degrees C without affecting the bulk MAX phase structure. However, during the hydrothermal treatment (HT) a thin oxide layer - found to play an important role in the reaction's selectivity- was evidenced by X-ray photoelectron spectroscopy. We thus conclude that the MOx species are responsible for the CH4 activation, while the Ti3SiC2 surface is responsible for the high selectivity to formaldehyde indicating that, Ti3SiC2 has great potential for designing innovative catalysts for direct oxidation of methane using molecular oxygen and at atmospheric pressure.

By experiment we evaluated the longitudinal magnetostriction on cylindrical samples of MnZn ferrite. Starting from the idea that the magnetostriction phenomenon is closely related to the magnetization phenomenon of the ferromagnetic sample, by plotting the magnetostriction curve it is possible to extract the magnetization curve of the ferromagnetic material and to evaluate the saturation magnetization of the material and the demagnetizing factor of the sample. At the same time, the paper suggests a way to study the dynamics of the movement of the magnetic domain walls in the sample, by examining the resonance curve at each point on the magnetization curve.

The characteristics of the anode material play a critical role in the efficiency of microbial fuel cells (MFCs). Among anode modification strategies, carbon-based nanostructures have been successfully used, due to their improved surface area, conductivity, and biocompatibility. In the efforts to improve MFC performance, nitrogen doping of carbon nanostructures (NDCNs) introduces more reactive sites on the anode surface that enhance both the electron transfer rate and microbial adhesion. In this aim, the present study focuses on the influence of anode modification with NDCNs with different morphologies (nanotubular and globular), obtained through direct carbonization of polypyrrole nanostructures, on the microbial diversity of anodic biofilms and microbial fuel cell performance. XPS analyses show similar N content and functionality for both NCDN morphologies, with graphitic nitrogen as the dominant surface nitrogen type, followed by pyridinic and pyrrolic nitrogen. Results indicate the best MFC performance of NCDN-modified anodes was obtained in the case of NCDN with nanotubule-like morphologies (43.2 mW m-2) compared to globular NDCN (29.3 mW m-2). The improved performance of MFC might be assigned with NCDN with nanotubule-like morphology that assembles onto the carbon cloth into a porous three-dimensional architecture due to the cross-connection of individual particles, forming micro-cavities and pits which, along with an improved nanoscale spatial order, create a continuous pathway for electron transport and as a consequence a better electrical conductivity (1.32 S cm-1) compared to the globular one (0.59 S cm-1). Thus, our study shows that the morphology of the sample is a deciding factor that contribute to the improved performance of MFCs along with nitrogen content and functionality.