National Institute Of Materials Physics - Romania

Ceria materials doped by Gd and/or Pr were prepared by a precipitation route and calcined in air at 500 and 900 degrees C. The effects of doping and thermal treatment on the materials' surfaces were studied by X-ray photoelectron and Raman spectroscopies. The redox properties were investigated using temperature-programmed reduction experiments in H-2 and CH4 followed by temperature-programmed oxidation in O-2. The catalytic properties of these materials in CH4/H2O reaction in the absence/presence of H2S were evaluated at 750 degrees C in a large excess of CH4 with respect to H2O. The materials were classified by order of reactivity as follows: CPO > CGPO > CeO2 > CGO, which can be primarily related to the surface area variation. Comparing the activity per m(2) of various samples indicates that the catalytic activity is correlated with the Ce3+ concentration at the surface as measured by XPS. Gd-doped and undoped samples exhibit the highest surface Ce3+ concentration as well as the highest activity in SMR per m(2), while Pr-doped samples are the least active (activity per m(2)) with the lowest surface Ce3+ concentrations. H2S has a sharp promoting effect on the catalytic behavior of ceria-based materials, improving the production of H-2 by almost one order of magnitude.

Mixed manganese iron oxides (Mn/Fe/O) as heterogeneous catalysts were prepared by hydrothermal treatment and citrate methods to be tested in the oxidation of p-xylene (PX) using as oxidation agent molecular oxygen, hydrogen peroxide, and tert-butyl hydroperoxide. Preparation of mixed Mn-Fe oxide by the citrate method releases materials with smaller particle size and lower degree of crystallinity as compared with the hydrothermal one, which further leads to a higher activity toward the oxidation of PX. A conversion of PX of 98% and a yield in p-toluic acid of 93% were obtained in the presence of Mn/Fe/O prepared by the citrate method using tert-butyl hydroperoxide as an oxidizing agent. (C) 2017 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

The catalytic methanolysis of the chemical warfare nerve agents soman, sarin, and VX was investigated by using Cu or Zn complexes. Although VX withstood decontamination, the decomposition yield being around 96%, the soman and sarin deposited on different surfaces were almost fully destroyed under ambient conditions. The catalytic tests performed on a wide range of contaminated surfaces confirm the activity of the investigated catalytic systems, these complexes being suitable, from an economical point of view, for use in the formulation of a possible decomposition kit with military or civilian applicability. (C) 2017 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

This contribution concerns the catalytic activity of functional layered double hydroxides (LDHs) for 1,4-addition of n-octanol to 2-propenonitrile aiming to investigate the influence of the organic interlayer anion nature on their physico-chemical and catalytic performances. Two series of functional LDHs, e.g. Mg2.5Al, and Zn2.5Al respectively, were synthesized by co-precipitation at pH 9.5 using a metal nitrates M2+ (NO3)(2)center dot 6H(2)O (M2+ = Mg, Zn), Al(NO3)(3)center dot 9H(2)O solution, an organic acid sodium salt (e.g. sodium dodecyl sulfate (NaDS), sodium laurate (NaL), or sodium stearate (NaS)) and NaOH solution for pH adjustment. XRD, DRIFTS and DR-UV-Vis-NIR characterizations indicated a better intercalation of DS in the interlayer region compared to L or S. The catalytic activity of these solids was related to both their organophilic character and basicity, Mg2.5Al-DS samples, which were more basic, showed a higher activity than Zn2.5Al-DS.

We investigate the down- and up-conversion properties of Er (0.3, 1 and 3%)-CeO2 and Er(1%)Yb(20%)-CeO2 nanoparticles by use of ns pulsed monochromatic excitation. The emission spectra were recorded in the visible to near-infrared range (500-1100 nm) under ultraviolet, visible (490 and 650 nm) and near infrared (790, 971/977 and 1470 nm) up-conversion excitations as well as X-ray excitation. The structural properties were characterized by X-ray diffraction, Raman, Diffuse Reflectance UV/Vis and Diffuse Reflectance Fourier Transform Infrared spectroscopies. The role of CeO2 charge transfer band as a level selective antenna sensitizer, the dopant induced oxygen vacancies and the effect of Er concentration on the overall emission properties are highlighted. The mechanisms involved in the up-conversion emission in Er-CeO2 and Er,Yb-CeO2 are analysed in terms of up-conversion excitation spectra, up-conversion emission decays and evolution of the red to green emission ratio with Er concentration and delay after the laser pulse. Our findings are also discussed in the context of a comprehensive literature survey regarding the actual stage of research on the luminescence of Er and Er,Yb doped CeO2 and their possible applications. (C) 2017 Elsevier B.V. All rights reserved.

Local symmetry distortion by Li addition is acknowledged as an effective strategy for enhancing the luminescence of lanthanide (Ln) doped into a wide range of lattice hosts. Despite extensive literature, direct evidence that supports Li-induced modification of the local crystal-field at the Ln sites is still missing. Herein, we show that the emission enhancement by Li addition in Ln,Li-Y2O3 is due to improved crystallization and not to local structure distortion. Our approach is based on the premise that any distortion/lowering of the local symmetry would reflect into the alteration of the emission shapes and shortening of the emission decays. To this aim, we have extensively investigated the evolution with Li addition and calcination temperature of down (optical and X-ray induced) and up-conversion (UPC) emission of Ln-Y2O3 measured across the visible to near-infrared range. First, a center to center (corresponding to Ln in the C-2 and S-6/C-3i sites of the cubic Y2O3 lattice) as well as global comparison of the emission properties of Li free and Li codoped Y2O3 are presented by use of Eu, Sm, Tb and Dy as local probes in the visible range. Next, the effect of Li on the up-conversion emission of Er-Y2O3 is analyzed in terms of UPC pathways, emission shape and intensity, decays and excitation spectra. It is concluded that Li addition does not change either the local structure around C-2 or S-6 Ln centers or the relative contribution of these. Moreover, it is found that the effects of Li doping on the emission properties of Ln-Y2O3 are like extending the calcination temperature of Li-free Ln-Y2O3 from 800 degrees C to similar to 1000-1100 degrees C. Additionally, a relatively intense 1500 to 980 nm UPC emission is evidenced for the first time for Er-Y2O3, while a relatively intense "emission around 1500 nm was measured under X-ray excitation. Taken together, our findings highlight the need for revisiting the traditional optimization strategy based on Li modification but also the promise of Er-Y2O3 nanoparticles for optical/X-ray applications in the near-infrared range.

Development of new sensitive materials by different synthesis routes in order to emphasize the sensing properties for hazardous H2S detection is one of a nowadays challenge in the field of gas sensors. In this study we obtained mesoporous SnO2-CuWO4 with selective sensitivity to H2S by an inexpensive synthesis route with low environmental pollution level, using tripropylamine (TPA) as template and polyvinylpyrrolidone (PVP) as dispersant/stabilizer. In order to bring insights about the intrinsic properties, the powders were characterized by means of a variety of complementary techniques such as: X-Ray Diffraction, XRD; Transmission Electron Microscopy, TEM; High Resolution TEM, HRTEM; Raman Spectroscopy, RS; Porosity Analysis by N-2 adsorption/desorption, BET; Scanning Electron Microscopy, SEM and X-ray Photoelectron Spectroscopy, XPS. The sensors were fabricated by powders deposition via screen printing technique onto planar commercial Al2O3 substrates. The sensor signals towards H2S exposure at low operating temperature (100 degrees C) reaches values from 10(5) (for SnWCu600) to 10(6) (for SnWCu800) over the full range of concentrations (5-30 ppm). The recovery processes were induced by a short temperature trigger of 500 degrees C. The selective sensitivity was underlined with respect to the H2S, relative to other potential pollutants and relative humidity (10-70% RH). (C) 2017 Elsevier B.V. All rights reserved.

A new facile template method for the preparation of Ni, Co doped ZrO2 self-assembled electrocatalysts for oxygen reduction reaction was employed. The effect of the Ni and Co incorporation into ZrO2 lattice on the structural, texturaL surface chemistry and its activity on ORR was emphasized. As X-ray diffraction reveals, the pseudo-cubic lattice of the tetragonal ZrO2 polymorph (t-ZrO2) is stabilized when Ni and Co are co-doping ZrO2. The results indicate that the synergetic effects arisen from the intimate electronic interaction of the mixed oxides present in the lattice of the zirconia phase, i.e. Nil-xCoxO (or NiO and CoO) in NCZ enhance the electrocatalytic activity of the catalyst. (C) 2017 Elsevier B.V. All rights reserved.