National Institute Of Materials Physics - Romania

The development of robust, safe, cost-effective and efficient photocatalytic systems for water splitting should take into account the presence of a proper and powerful photon absorber and an efficient, low-cost and earth-abundant electrocatalyst to perform the reaction at high conversions. In this study, Ni-Zn/TiO(2)ternary composites with high photocatalytic activity for water splitting under UV irradiation were successfully prepared via a simple and low-cost deposition-precipitation route. Thus, different Ni : Zn molar ratios (1 : 0, 1 : 1, 3 : 1, 6 : 1, 9 : 1, and 0 : 1) were deposited on TiO(2)in order to reach a total metal loading of 50 wt. %. The obtained composites were characterized using several techniques, such as: X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The most active synthesized composite, namely Ni-Zn/TiO2(9 : 1), exhibits H(2)generation rate above 17 mmols g(-1) h(-1), which is nearly one thousand times higher than that obtained with TiO(2)Evonik P25. Our study demonstrates that TiO(2)becomes a degenerated semiconductor in the presence of Ni and ZnO, with remarkable photocatalytic properties. Thus, the obtained results can open new opportunities in the preparation of very active materials for hydrogen production based on the optimization of three-component structures.

The catalytic activity of a series of vanadium aluminophosphates catalysts prepared by sol-gel method followed by combustion of the obtained gel was evaluated in glycerol conversion towards methanol. The materials were characterized by several techniques such as X-ray diffraction (XRD), UV-vis, Fourier-transform infrared (FTIR), Raman and X-ray photoelectron (XPS) spectroscopies. The amount of vanadium incorporated in aluminophosphates framework played an important role in the catalytic activity, while in the products distribution the key role is played by the vanadium oxidation state on the surface. The sample that contains a large amount of V(4+)has the highest selectivity towards methanol. On the sample with the lowest vanadium loading the oxidation path to dihydroxyacetone is predominant. The catalyst with higher content of tetrahedral isolated vanadium species, such V5APO, is less active in breaking the C-C bonds in the glycerol molecule than the one containing polymeric species.

This study reports on the results obtained after doping the [CH3NH3](0.94)[C3N2H5](0.06)PbI2.6Cl0.4 mixt halide perovskite with europium or antimony (Eu3+/Sb3+) at the 'B site'. This way two new complex compounds were obtained, [CH3NH3](0.94)[C3N2H5](0.06)Pb1-yByI2.6Cl0.4 (B = Eu or Sb and y = 0-0.05) as perovskite precursor solutions and deposited as thin films. The properties of the perovskite films were investigated by various characterization techniques: x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-vis spectroscopy while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. We find that doping the mixt halide perovskite with very small quantities of Sb improves the quality of the perovskite films and further improves the stability of perovskite solar cells.

To improve the catalytic performance of an active layered double hydroxide (LDH)-derived CuCeMgAlO mixed oxide catalyst in the total oxidation of methane, it was promoted with different transition-metal cations. Thus, two series of multicationic mixed oxides were prepared by the thermal decomposition at 750 degrees C of their corresponding LDH precursors synthesized by coprecipitation at constant pH of 10 under ambient atmosphere. The first series of catalysts consisted of four M(3)CuCeMgAlO mixed oxides containing 3 at.% M (M = Mn, Fe, Co, Ni), 15 at.% Cu, 10 at.% Ce (at.% with respect to cations), and with Mg/Al atomic ratio fixed to 3. The second series consisted of four Co(x)CuCeMgAlO mixed oxides withx= 1, 3, 6, and 9 at.% Co, while keeping constant the Cu and Ce contents and the Mg/Al atomic ratio. All the mixed oxides were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with X-ray energy dispersion analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption at -196 degrees C, temperature-programmed reduction under hydrogen (H-2-TPR), and diffuse reflectance UV-VIS spectroscopy (DR UV-VIS), while thermogravimetric and differential thermal analyses (TG-DTG-DTA) together with XRD were used for the LDH precursors. The catalysts were evaluated in the total oxidation of methane, a test reaction for volatile organic compounds (VOC) abatement. Their catalytic performance was explained in correlation with their physicochemical properties and was compared with that of a reference Pd/Al(2)O(3)catalyst. Among the mixed oxides studied, Co(3)CuCeMgAlO was found to be the most active catalyst, with a temperature corresponding to 50% methane conversion (T-50) of 438 degrees C, which was only 19 degrees C higher than that of a reference Pd/Al(2)O(3)catalyst. On the other hand, this T(50)value was ca. 25 degrees C lower than that observed for the unpromoted CuCeMgAlO system, accounting for the improved performance of the Co-promoted catalyst, which also showed a good stability on stream.

Palladium is one of the most efficient metals for the hydrogenation of organic compounds. However, when molecules, such as nitroaromatics, with several reducible functionalities, are hydrogenated, Pd, like any other very active metal, such as nickel or platinum, often behaves unselectively. One strategy to render Pd more selective is to choose the proper support. Herein, we show that MAX phase powders of Ti3SiC2, Ti2AlC, or Ti3AlC2 can chemoselectively hydrogenate 4-nitrostyrene to 4-aminostyrene, with 100% selectivity, at around 3-4% conversion. To boost the latter, we loaded Ti3SiC2 with 0.0005 wt % Pd and increased the conversion to 100% while maintaining the 4-AS selectivity at >90%. By optimizing the Pd loading, we were also able to increase the turnover frequency 100-fold relative to previous literature results. The identification of this highly efficient and chemoselective system has broad implications for the design of cost-effective, earth-abundant, nontoxic, metal catalysts, with ultralow noble metal loadings.

Mesoporous CeO2:Mn3O4 materials (3:7 and 7:3 molar ratio) were prepared by co-precipitation and deposited as porous thick films over alumina (Al2O3) planar substrate provided with Pt meander. The aim was oriented towards detecting low levels methane (CH4) at moderate operating temperatures. Herein we demonstrated that the sensitivity of catalytic micro-converters (CMCs) towards a given peak of CH4 concentration corresponds to specific gas-surface interaction phenomena. More precisely, a transition from thermal conductivity to combustion rate is likely to occur when CMCs are operated under real atmospheric conditions (normal pressure, presence of relative humidity, and constant operating temperature). The response to CH4 was analyzed over different gas flows and different gas concentrations under the same operating regime. The materials were fully characterized by adsorption-desorption isotherms, H-2-Temperature Programmed Reduction (H-2-TPR), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Raman spectroscopies. Thus, the applicative aspect of using CeO2:Mn3O4 as moderate temperature CMC for CH4 detection is brought to the fore.

In this study, the synergistic behavior of Ni species and bimodal mesoporous undoped SnO2 is investigated in oxygen evolution reactions (OERs) under alkaline conditions without any other modification of the compositional phases or using noble metals. An efficient and environmentally friendly hydrothermal method to prepare bimodal mesoporous undoped SnO2 with a very high surface area (>130 m(2) g(-1)) and a general deposition-precipitation method for the synthesis of well-dispersed Ni species on undoped SnO2 are reported. The powders were characterized by adsorption-desorption isotherms, TG-DTA, XRD, SEM, TEM, Raman, TPRH2, and XPS. The best NiSn composite generates, under certain experimental conditions, a very high TOF value of 1.14 s(-1) and a mass activity higher than 370 A g(-1), which are remarkable results considering the low amount of Ni deposited on the electrode (3.78 ng). Moreover, in 1 M NaOH electrolyte, this material produces more than 24 mA cm(-2) at an overpotential value of approximately +0.33 V, with only 5 wt % Ni species. This performance stems from the dual role of undoped SnO2, on the one hand, as a support for active and well-dispersed Ni species and on the other hand as an active player through the oxygen vacancies generated upon Ni deposition.

In this work, the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 (MAPbI(3)) was studied, aiming to improve the properties of perovskite films used in solar cells application. The surface morphology, the microstructure and the optical properties of the obtained films containing different Europium (Eu) concentrations were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, UV-vis spectroscopy and photoluminescence spectroscopy.

Graphene oxide has been synthesized, additionally derivatized with chloroacetic acid for increase the number of available carboxylic groups and further functionalized with crown-ether moieties. The thus obtained material was characterized by IR, thermal analysis, SEM, Raman, and XPS. Tests on adsorption of several metal cations showed that cooper and iron are more retained than potassium.

Correlating dopant distribution to its optical response represents a complex challenge for nanomaterials science. Differentiating the "true" clustering nature from dopant pairs formed in statistical distribution complicates even more the elucidation of doping-functionality relationship. The present study associates lanthanide dopant distribution, including all significant events (enrichment, depletion and surface segregation), to its optical response in upconversion (UPC) at the ensemble and single-nanoparticle level. A small deviation from the Er nominal concentration of a few percent is able to induce clear differences in Er UPC emission color, intensity, excited-state dynamics and ultimately, UPC mechanisms, across tetragonal to monoclinic phase transformation in rationally designed Er doped ZrO2 nanoparticles. Rare evidence of a heterogeneous dopant distribution leading to the coexistence of two polymorphs in a single nanoparticle is revealed by Z- and phase contrast transmission electron microscopy (TEM). Despite their spatial proximity, Er in the two polymorphs are spectroscopically isolated, i.e. they do not communicate by energy transfer. Segregated Er, which is well imaged in TEM, is absent in UPC, while the minor phase content overlooked by X-ray diffraction and TEM is revealed by UPC. The outstanding sensitivity of combined TEM and UPC emission to subtle deviations from uniform doping in the diluted concentration regime renders such an approach relevant for various functional oxides supporting lanthanide dopants as emitters.