National Institute Of Materials Physics - Romania

Herein, a new direct synthesis route leading to a mesoporous NiWO4 with crystalline framework and NiWO4 -graphene nanoplatelets (GNP) composite is reported. Ni and W assembled into a mesoporous tungstate type of symmetry by co-precipitation synthesis route and its composite with GNP were used as supports for electrocatalysts, with reduced Pt content (8 wt.%), in oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) in acidic medium. A comprehensive assessment of the modifications related to the crystalline and porous structures, morphological aspects as well as the surface chemistry aiming to explain the electrochemical properties was performed. It was found that the presence of GNP during the synthesis process leads, mainly, to the enhanced growth of NiWO4 nanocrystallites, as well as induces changes in the surface chemistry. The elec-trochemical results show that the introduction of GNPs into the NiWO4 composite support leads to a significant improvement in the activity of the Pt electrocatalyst in ORR and HOR compared to both initial NiWO4 and Pt/NiWO4 samples, as well as mechanical mixtures of these catalysts with carbon. Mass activity for hydrogen oxidation, determined in a mixed kinetic-diffusion controlled region, obtained on the 8 wt.% Pt/NiWO4-GNP catalyst was significantly higher compared to the commercial 20 wt.% Pt/C Quintech catalyst. Our comprehensive structural and surface chemistry assessments indicate this composite material as a viable electrocatalyst for PEMFCs using a broader type of fuels.& COPY; 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

In this study, we report the implications of the synthesis method on Gd2O3 sensitivity to CO2. The rare-earth oxide was prepared by wet chemical co-precipitation and by hydrothermal method. The obtained powders labelled Gd2O3-CoP and Gd2O3-HT were deposited as thick films over commercial Al2O3 substrates provided with Pt electrodes and a back-side heater. Both powders consist of the same crystallographic phase, with a significant difference appearing in selected area electron diffraction patterns, transmission electron microscopy images at higher magnification and X-ray diffraction spectra, with respect to the crystallization degree. The associated role in sensing properties is revealed via electrical resistance variations determined by CO2 concen-trations in the range between 400 and 3000 ppm and variable relative humidity between 0 and 50%RH, similar to the in-field atmosphere. The proposed CO2 interaction mechanism is based on phenomenological in-vestigations which highlight the electronic affinity variation as the effect of dipoles induced by the in-field conditions on the Gd2O3 surface.

The oxidation of methionine side chain residues in proteins provides a great diversity of possible oxidation mechanisms dictated, among others, by the oxidizing species, solvent properties, and protein structure. The oxidation behavior of a series of short acetylated synthetic peptides, Ac-GMG, Ac-GGMGG and Ac-GGGMGGG, was investigated by differential pulse and square wave voltammetry, in a wide pH range, at glassy carbon electrode. It was found that always the first oxidation step represents the one-electron oxidation of thioether moiety with the formation of a radical cation. Following this, depending on the experimental condi-tions and side chain position of methionine, the radical is stabilized by the nucleophilic attack of water or by catalytic support of the neighboring carbonyl and amide groups in an intermediate structure, finally converted in methionine sulfoxide which can be further oxidized, at more positive potential, into methionine sulfone. For Ac-GGGMGGG, at pH 8.0, the amino and amide groups are active involved in the oxidation process and the electrode reaction takes place with proton transfer

Hybrid layers consisting of Fe oxide, Fe hydroxide, and nitrogen doped graphene-like platelets have been synthesized by an eco-friendly laser-based method for photocatalytic applications. The complex composite layers show high photodecomposition efficiency towards degradation of antibiotic molecules under visible light irradiation. The photodecomposition efficiency was investigated as a function of relative concentrations of base materials, Fe oxide nanoparticles and graphene oxide platelets used for the preparation of target dispersions submitted to laser irradiation. Although reference pure Fe oxide/Fe hydroxide layers have high absorption in the visible spectral region, their photodecomposition efficiency is negligible under the same irradiation conditions. The high photocatalytic decomposition efficiency of the nanohybrid layer, up to 80% of the initial antibiotic molecules was assigned to synergistic effects between the constituent materials, efficient separation of the electron-hole pairs generated by visible light irradiation on the surface of Fe oxide and Fe hydroxide nanoparticles, in the presence of conducting graphene-like platelets. Nitrogen doped graphene-like platelets contribute also to the generation of electron-hole pairs under visible light irradiation, as demonstrated by the photocatalytic activity of pure, reference nitrogen doped graphene-like layers. The results also showed that adsorption processes do not contribute significantly to the removal of antibiotic molecules from the test solutions. The decrease of the antibiotic concentration under visible light irradiation was assigned primarily to photocatalytic decomposition mechanisms.

Hydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 degrees C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 degrees C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution transmission electron microscopy. We discovered that the catalytic reaction is driven by surface tin-oxide phases, which protects the underlying Ni atoms from irreversible chemical modifications, increasing the catalyst durability. Moreover, we found that Sn content plays a key role in enhancing the H2 selectivity, with respect to secondary products such as CO2. These findings open new perspectives for the engineering of scalable and low-cost catalysts for hydrogen production.

Lanthanide (Ln) co-doped transition metal (TM) upconversion (UC) co-doped systems are being intensively investigated for their exciting applications in photonics, bioimaging, and luminescence thermometry. The presence of TM, such as Mo6 + /W6 +, Mn2 +, or Fe3 + determines significant changes in Ln UC emission, such as intensity enhancement, colour modulation, and even the alteration of the photon order. The current mechanism assumes a ground-state absorption/excited-state absorption (ESA/GSA) in TM-Yb dimer followed by direct energy transfer to Er/Tm excited states. We revisit this mechanism by addressing two issues that remain ignored: a dynamical approach to the investigation of the upconversion mechanism and the intrinsic chemical complexity of co-doped TM, Ln systems. To this aim, we employ a pulsed, excitation variable laser across a complete set of UC measurements, such as the emission and excitation spectra and emission decays and analyze multiple grains with transmission electron microscopy (TEM). In the Mo co-doped garnet, the results sustain the co-existence of Mo-free garnet and Mo oxide impurity. In this Mo oxide, the Er upconversion emission properties are fully explained by a relatively efficient sequential Yb to Er upconversion process, with no contribution from Yb-Mo dimer sensitization.

In the present work, nanocrystalline NixCo1-xFe2O4 oxides with average crystallite size between 11 nm and 111 nm have been analyzed by Mossbauer spectroscopy, hysteresis loops, field cooled (FC) and zero field cooled (ZFC) magnetization measurements. A core-shell model has been proposed. Accordingly, the Mossbauer spectra evidence a ferrimagnetic core and a disordered shell (spin-glass), the latter increasing with Ni concentration. Hysteresis curves reveal the ferromagnetic nature of the investigated compounds and transformation from single- to multi-domain behaviour at a critical particle size dependent on Ni2+ ion concentration. The magnetic properties of finest powders (average crystallite size similar to 11 nm) are the most sensitive to the Ni2+ ions content. A general increase in the coercive field, H-C, with reducing temperature according to the modified Kneller's formula H-c(T) = H-c(0)[1-(T/T-B)(beta) where beta = 0.45 occurs. A high saturation magnetization of about 90 emu/g and an increase in H-C from about 0.3 kOe at 300 K to 7 kOe at 10 K have been observed for the sample Ni0.1Co0.9Fe2O4 (x = 0.1). Increasing magnetization and coercive field with reducing temperature are also explained within the core shell model. FC and ZFC data show strong dependence of the magnetic properties on crystallite size and concentration of Ni2+ ions.

In the present work, nanocrystalline NixCo1-xFe2O4 oxides with average crystallite size between 11 nm and 111 nm have been analyzed by Mossbauer spectroscopy, hysteresis loops, field cooled (FC) and zero field cooled (ZFC) magnetization measurements. A core-shell model has been proposed. Accordingly, the Mossbauer spectra evidence a ferrimagnetic core and a disordered shell (spin-glass), the latter increasing with Ni concentration. Hysteresis curves reveal the ferromagnetic nature of the investigated compounds and transformation from single- to multi-domain behaviour at a critical particle size dependent on Ni2+ ion concentration. The magnetic properties of finest powders (average crystallite size similar to 11 nm) are the most sensitive to the Ni2+ ions content. A general increase in the coercive field, H-C, with reducing temperature according to the modified Kneller's formula H-c(T) = H-c(0)[1-(T/T-B)(beta) where beta = 0.45 occurs. A high saturation magnetization of about 90 emu/g and an increase in H-C from about 0.3 kOe at 300 K to 7 kOe at 10 K have been observed for the sample Ni0.1Co0.9Fe2O4 (x = 0.1). Increasing magnetization and coercive field with reducing temperature are also explained within the core shell model. FC and ZFC data show strong dependence of the magnetic properties on crystallite size and concentration of Ni2+ ions.

Yttrium iron garnet nanoparticles were exposed to mechanochemical activation by high-energy ball milling for 0, 2, 4, 8 and 12 h, with and without graphene nanoparticles. The samples were subsequently characterized by Mo center dot ssbauer spectroscopy, X-ray powder diffraction (XRPD), magnetic measurements and optical diffuse reflec-tance spectroscopy. Examination of the quadrupole doublet's abundance as function of ball milling time indi-cated that graphene slowed down the precipitation of the yttrium iron perovskite (yttrium orthoferrite) phase. The increased linewidth of the doublet showed that the carbon from graphene preferentially entered the lattice of the yttrium orthoferrite. The saturation magnetization decreased with decreasing particle size for prolonged milling due to the occurrence of the antiferromagnetic hematite phase. The enhanced absorption in the infrared region could be associated with the incorporation of carbon from graphene in the lattice of the yttrium ortho-ferrite. The results are interesting for sensing and microwave applications.

A sensor for the enzymatic activity and inhibition of the 20S proteasome was developed by immobilizing the synthetic peptide ABZ-VVSYAMG-(O2Oc)2-OH at Au electrodes. The detection principle is based on the elec-troactivity of ABZ, part of the ABZ-VVSY-OH moiety released from the peptide upon 20S proteasome chymo-trypsin action. The peptide was immobilized on a para-amino thiophenol (PATP) self-assembled monolayer on Au electrode by cross-linking its amino group to the -(O2Oc)2-OH moiety of the peptide (Au/PATP/peptide). The immobilization of the peptide and its interaction with 20S proteasome was investigated by SEM, QCM, SPR, ATR-FTIR and electrochemistry. The activity of 20S proteasome was assessed electrochemically by cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) after the immersion Au/PATP/peptide in 20S proteasome solution. CV study showed a decrease in both capacitive and faradaic currents corresponding to the ABZ-VVSY-OH removal, allowing the quantification of the 20S proteasome activity. The EIS study revealed that the resis-tance corresponding to charge transfer reactions at the peptide/solution interface correlated to the ABZ redox reaction, decreased linearly with increasing the incubation time in 20S proteasome solution. The perfected assay was applied for the investigation of the inhibitory effect of one synthetic, bortezomib, and two naturally occurring, epoxomicin, and lactacystin inhibitors.