National Institute Of Materials Physics - Romania

Two neutral copper(I) halide complexes ([Cu(BTU)(2)X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N '-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (H-1 and C-13), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH horizontal ellipsis X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 x 10(-7) S.cm(-1) was achieved at 430 K for the chloro-complex and 1.37 x 10(-6) S.cm(-1) at 440K for the related bromo-complex.

Methanol (CH3OH) oxidation offers a promising avenue for transitioning to clean energy, particularly in the field of direct methanol fuel cells (DMFCs). However, the development of efficient and cost-effective catalysts for the methanol oxidation reaction (MOR) remains a critical challenge. Herein, we report the exceptional electrocatalytic activity and stability of Ni3Sn4 toward MOR in acidic media, achieving a performance comparable to that of commercial Pt/C catalysts. Our catalyst design incorporates Earth-abundant Ni and Sn elements, resulting in a material that is 1800 times more cost-effective than Pt/C. Density functional theory (DFT) modeling substantiates our experimental findings, shedding light on the favorable reaction mechanisms and kinetics on the Ni3Sn4 surface. Additionally, the as-synthesized Ni3Sn4 electrocatalyst demonstrates commendable durability, maintaining its electrocatalytic activity even after prolonged exposure to harsh acidic conditions.

Methanol (CH3OH) oxidation offers a promising avenue for transitioning to clean energy, particularly in the field of direct methanol fuel cells (DMFCs). However, the development of efficient and cost-effective catalysts for the methanol oxidation reaction (MOR) remains a critical challenge. Herein, we report the exceptional electrocatalytic activity and stability of Ni3Sn4 toward MOR in acidic media, achieving a performance comparable to that of commercial Pt/C catalysts. Our catalyst design incorporates Earth-abundant Ni and Sn elements, resulting in a material that is 1800 times more cost-effective than Pt/C. Density functional theory (DFT) modeling substantiates our experimental findings, shedding light on the favorable reaction mechanisms and kinetics on the Ni3Sn4 surface. Additionally, the as-synthesized Ni3Sn4 electrocatalyst demonstrates commendable durability, maintaining its electrocatalytic activity even after prolonged exposure to harsh acidic conditions.

Historically, titanium dioxide (TiO2) has been one of the most extensively studied metal oxide photocatalysts; however, it suffers from a large bandgap and fast charge recombination. We report the use of green, rapid, single-step continuous hydrothermal flow synthesis for the preparation of TiO2, and TiO2 hybrids with reduced graphene oxide (rGO) and/or N-doped carbon quantum dots (NCQDs) with significant enhancement in photocatalytic activity. Using a solar light generator under ambient conditions with no extra oxygen gas added, we observed the evolution reaction of the model pollutant (methylene blue) in real time. Tailoring of the light absorption to match that of the solar spectrum was achieved by a combination of materials of nano-TiO2 hybrids of nitrogen-doped carbon quantum dots and graphene in its reduced form with a photocatalytic rate constant of ca. 25 x 10(-5) s(-1). Using a diversity of state-of-the-art techniques including high-resolution transmission electron microscopy, transient photoluminescence, X-ray photoelectron spectroscopy and high accuracy, sophisticated hybrid density functional theory calculations we have gained substantial insight into the charge transfer and modulation of the energy band edges of anatase due to the presence of graphene or carbon dots, parameters which play a key role in improving drastically the photocatalytic efficiencies when compared to pristine titania. More importantly, we prove that a combination of features and materials displays the best photocatalytic behaviour. This performance is delivered in a greener synthetic process that not only produces photocatalytic materials with optimised properties and tailored visible light absorption and efficiency but also provides a path to industrialization.

Historically, titanium dioxide (TiO2) has been one of the most extensively studied metal oxide photocatalysts; however, it suffers from a large bandgap and fast charge recombination. We report the use of green, rapid, single-step continuous hydrothermal flow synthesis for the preparation of TiO2, and TiO2 hybrids with reduced graphene oxide (rGO) and/or N-doped carbon quantum dots (NCQDs) with significant enhancement in photocatalytic activity. Using a solar light generator under ambient conditions with no extra oxygen gas added, we observed the evolution reaction of the model pollutant (methylene blue) in real time. Tailoring of the light absorption to match that of the solar spectrum was achieved by a combination of materials of nano-TiO2 hybrids of nitrogen-doped carbon quantum dots and graphene in its reduced form with a photocatalytic rate constant of ca. 25 x 10(-5) s(-1). Using a diversity of state-of-the-art techniques including high-resolution transmission electron microscopy, transient photoluminescence, X-ray photoelectron spectroscopy and high accuracy, sophisticated hybrid density functional theory calculations we have gained substantial insight into the charge transfer and modulation of the energy band edges of anatase due to the presence of graphene or carbon dots, parameters which play a key role in improving drastically the photocatalytic efficiencies when compared to pristine titania. More importantly, we prove that a combination of features and materials displays the best photocatalytic behaviour. This performance is delivered in a greener synthetic process that not only produces photocatalytic materials with optimised properties and tailored visible light absorption and efficiency but also provides a path to industrialization.

We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.

Zinc substituted nickel-cobalt ferrites, i.e., ZnxNi0.8-xCo0.2Fe2O4 (x = 0.0, 0.05, 0.10 and 0.20) with average crystallite size 100 nm were synthesized by citrate-gel auto-combustion method to investigate effects of Zn2+ substitution on the structural and dielectric properties. Both X-ray diffraction (XRD) and IR spectroscopy studies confirms the formation of pure cubic spinel structure. Variation of lattice parameter infers Vegard's law linear dependence with the addition of Zn2+ concentration. The temperature-dependent behavior of dielectric and modulus spectra has been studied within the frequency range 100 Hz-100 kHz for different temperatures between 100 K and 400 K. It was concluded that the dielectric responses of ZnxNi0.8-xCo0.2Fe2O4 are found to be frequency dependent and thermally activated. Also, In the Zn doped ferrites variations of dielectric loss (tan d) and the imaginary part of electric modulus (M") show the presence of the non-Debye type of dielectric relaxation. Rise in Zinc concentration leads to a decrease in dielectric constant (e (r)) due to the declining of Fe3+-O-M2+ conducting network (M is Co or Ni). Here, we report a low loss tangent factor of the order of 8x10-3 0.6Zn(0.2)Co(0.2)Fe(2)O(4) make this composition suitable for high frequency-applications at room temperature. The activation energy is calculated from electric modulus formalism and DC electrical conductivity and found to increase with further substitution of Zn2+ concentration.

Zinc substituted nickel-cobalt ferrites, i.e., ZnxNi0.8-xCo0.2Fe2O4 (x = 0.0, 0.05, 0.10 and 0.20) with average crystallite size 100 nm were synthesized by citrate-gel auto-combustion method to investigate effects of Zn2+ substitution on the structural and dielectric properties. Both X-ray diffraction (XRD) and IR spectroscopy studies confirms the formation of pure cubic spinel structure. Variation of lattice parameter infers Vegard's law linear dependence with the addition of Zn2+ concentration. The temperature-dependent behavior of dielectric and modulus spectra has been studied within the frequency range 100 Hz-100 kHz for different temperatures between 100 K and 400 K. It was concluded that the dielectric responses of ZnxNi0.8-xCo0.2Fe2O4 are found to be frequency dependent and thermally activated. Also, In the Zn doped ferrites variations of dielectric loss (tan d) and the imaginary part of electric modulus (M") show the presence of the non-Debye type of dielectric relaxation. Rise in Zinc concentration leads to a decrease in dielectric constant (e (r)) due to the declining of Fe3+-O-M2+ conducting network (M is Co or Ni). Here, we report a low loss tangent factor of the order of 8x10-3 0.6Zn(0.2)Co(0.2)Fe(2)O(4) make this composition suitable for high frequency-applications at room temperature. The activation energy is calculated from electric modulus formalism and DC electrical conductivity and found to increase with further substitution of Zn2+ concentration.

Self-powered UV sensing has enormous potential in military and civilian applications. However, achieving high responsivity and fast response/recovery time presents significant challenges. Self-powered photodetectors (PDs) have several advantages over traditional PDs, including higher sensitivity, lower power consumption, and simpler design. This study introduces a breakthrough self-powered PD that uses a Schottky junction of 2D alpha-MoO3/iridium (Ir)/Si ultrathin film to detect 365 nm light at 0 V bias through using atomic layer deposition (ALD) and sputtering systems. The PD response is enhanced by plasmonic Ir-induced hot carriers, enabling detection in a mere 0.1 ms. Incorporating a 4 nm Ir layer boosts the responsivity from 0 to 34 A W-1, and the external quantum efficiency is elevated from 0 to 7E11 under 365 nm light illumination. It also has a high I-ON/I-OFF ratio of 11.22E4 at 0 V. These results make the MoO3/4 nm Ir/Si structure an interesting option for self-powered PDs with high efficiency, and the use of a simple ALD system for large-scale fabrication of 2D alpha-MoO3 on hot carrier Ir plasmonic layer. The findings of this research hold tremendous promise in the field of UV sensing and can lead to exciting developments in military and civilian technology.

In this work, we demonstrate that solution-processed In2Se3 nanosheets exhibit exceptional selectivity and sensitivity to NO2 gas, making them a promising candidate for gas detection systems. Theoretical simulations and surface-science experiments reveal the unique surface properties of In2Se3 nanosheets, which prevent physisorption of oxygen, carbon monoxide, and carbon dioxide, making them remarkably stable towards oxidation and CO-poisoning. Moreover, we show that NO2 molecules adsorb stably on In2Se3 nanosheets, particularly on Se vacancies, even at high temperatures. The coadsorption of water further enhances NO2 sticking on the In2Se3 surface, making it an ideal material for gas sensing applications in humid and harsh environments. The fabricated In2Se3 gas sensors exhibit excellent and reversible sensing response to NO2 gas, with a limit of detection of 5 ppb at 300 degrees C, and a highly selective response to NO2 compared to other gases and volatile organic compounds. Our sensors outperform other two-dimensional (2D) semiconductors, metal oxides, and their heterostructures, thanks to the unique surface properties of In2Se3 nanosheets. Importantly, the number of layers and termination of the surface almost have no impact on the sensing performance of In2Se3, which is advantageous for practical applications. The high sensitivity, selectivity, and stability of In2Se3 nanosheets make them an exciting platform for the fabrication of high-performance gas sensors, particularly in harsh environments, such as industrial settings or outdoor monitoring. Moreover, our solution processing approach enables scalable production of the sensors. Additionally, their unique surface properties make them an attractive candidate for developing complex composite nanostructures with tailored gas sensing characteristics for various applications.