Reduction-Driven 3D to 2D Transformation of Cu Nanoparticles.

The interaction between metal and metal oxides at the nanoscale is of uttermost importance in several fields, thus its enhancement is highly desirable. In catalysis, the performance of the nanoparticles is dependent on a wide range of properties, including its shape that is commonly considered stable during the catalytic reaction. In this study, highly reducible CeO2-x nanoparticles are synthesized aiming to provide Cu/CeO2-x nanoparticles, which are classically active catalysts for the CO oxidation reaction. It is observed that the Cu nanoparticles shape changes during reduction treatment (prior to the CO oxidation reaction) from a nearly spherical 3D to a planar 2D shape, then enhances the Cu-CeO2-x interaction. The spread of the Cu nanoparticles over the CeO2-x surface during the reduction treatment occurs due to the minimization of the total system energy. The shape change is accompanied by migration of O atoms from CeO2 surface to the border of the Cu nanoparticles and the change from the Cu0 to Cu+1 state. The spreading of the Cu nanoparticles influences on the reactivity results toward the CO oxidation reaction since it changes the local atomic order around Cu atoms. The results show a timely contribution for enhancing the interaction between metal and metal oxide.

Tuning the structure and magnetic behavior of Ni-Ir-based nanoparticles in ionic liquids.

We report on a simple preparation of extremely small diameter (ca. 2 nm) Ni-Ir-based NPs using Ni(COD)2 and [Ir(COD)OCH3]2 in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm·NTf2). The prepared NPs had either core-shell-like or alloy-like structures with the presence of Ni,Ir-oxides, depending on the synthetic approach. X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and magnetic measurements are combined to describe the influence of nanostructure on the magnetic behavior of these nanosystems. The present findings reveal that the alloy NPs display a disordered magnetic state, similar to a spin glass (SG)-like system (Tf = 7.2 K). Core-shell NPs are formed by a magnetically blocked/unblocked core with a magnetically disordered shell as deduced from the two magnetic responses peaking at TB = 75 K and Tf = 5.8 K. Coupling at the core-shell interface leads to an exchange bias revealed at low temperature as horizontal shifts in the hysteresis loops of 0.12 kOe at 2 K.

Hydrophobic effects on supported ionic liquid phase Pd nanoparticle hydrogenation catalysts.

Hybrid organosilicas prepared by sol-gel processes using 1-n-butyl-3-(3-trimethoxysilylpropyl)-imidazolium cations associated with hydrophilic and hydrophobic anions can be easily decorated with well dispersed and similar size (1.8-2.1 nm) Pd nanoparticles (Pd-NPs) by simple sputtering-deposition. Higher Pd concentration at the surface compared to the deeper region is obtained in the supports with smaller pore diameter (containing hydrophobic ILs) than in supports with the largest pore diameter (containing hydrophilic ILs). The IL hydrophobicity plays a central role in the hydrogenation of dienes by controlling the diene access to NP surface active sites.

Açaí (Euterpe oleracea Mart.) green synthesis of silver nanoparticles: antimicrobial efficacy and ecotoxicological assessment.

The synthesis of silver nanoparticles (AgNPs) is usually based on expensive methods that use or generate chemicals that can negatively impact the environment. Our study presents a simple one-step synthesis process for obtaining AgNP using an aqueous extract of Amazonian fruit açai (Euterpe oleracea Mart.) as the reducing and stabilizing agents. The bio-synthesized AgNP (bio-AgNP) were comprehensively characterized by diverse techniques, and as a result, 20-nm spherical particles (transmission electron microscopy) were obtained. X-ray diffraction analysis (XRD) confirmed the presence of crystalline AgNP, and Fourier-transform infrared spectroscopy (FT-IR) suggested that polyphenolic compounds of açaí were present on the surface. The bio-AgNP showed antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii. In Caenorhabditis elegans exposed to 10 µg/L bio-AgNP for 96 h, there were no significant effects on growth, reproduction, or reactive oxygen species (ROS) concentration; however, there was an increase in superoxide dismutase (SOD) and glutathione-S-transferase (GST) enzymatic activity. In contrast, when worms were exposed to chemically synthesized AgNP (PVP-AgNP), an increase in ROS, SOD, and GST activity and a reduction in oxidative stress resistance were observed. In conclusion, our study not only showcased the potential of açaí in the simple and rapid production of AgNP but also highlighted the broad-spectrum antimicrobial activity of the synthesized nanoparticles using our protocol. Moreover, our findings revealed that these AgNPs exhibited reduced toxicity to C. elegans at environmentally realistic concentrations compared with PVP-AgNP.

Potential Control of Oxygen Non-Stoichiometry in Cerium Oxide and Phase Transition Away from Equilibrium.

Cerium oxide (ceria, CeO2) is a technologically important material for energy conversion applications. Its activities strongly depend on redox states and oxygen vacancy concentration. Understanding the functionality of chemical active species and behavior of oxygen vacancy during operation, especially in high-temperature solid-state electrochemical cells, is the key to advance future material design. Herein, the structure evolution of ceria is spatially resolved using bulk-sensitive operando X-ray diffraction and spectroscopy techniques. During water electrolysis, ceria undergoes reduction, and its oxygen non-stoichiometry shows a dependence on the electrochemical current. Cerium local bonding environments vary concurrently to accommodate oxygen vacancy formation, resulting in changes in Ce-O coordination number and Ce3+/Ce4+ redox couple. When reduced enough, a crystallographic phase transition occurs from α to an α' phase with more oxygen vacancies. Nevertheless, the transition behavior is intriguingly different from the one predicted in the standard phase diagram of ceria. This paper demonstrates a feasible means to control oxygen non-stoichiometry in ceria via electrochemical potential. It also sheds light on the mechanism of phase transitions induced by electrochemical potential. For electrochemical systems, effects from a large-scale electrical environment should be taken into consideration, besides effective oxygen partial pressure and temperature.

Artificial cerium-based proenzymes confined in lyotropic liquid crystals: synthetic strategy and on-demand activation.

Inorganic nanoparticles that mimic the activity of enzymes are promising systems for biomedical applications. However, they cannot distinguish between healthy and damaged tissues, which could cause undesired effects. Natural enzymes avoid this drawback via activation triggered by specific biochemical events in the body. Inspired by this strategy, we proposed an artificial cerium-based proenzyme system that could be activated to a superoxide dismutase-like form using H2O2 as the trigger. To achieve this goal, an innovative and easy strategy to synthesize Ce(OH)3 nanoparticles as artificial proenzymes was developed using a lyotropic liquid crystal composed of phytantriol, which was essential to maintain their stability at physiological pH. The transmission electron microscopy measurements showed that the Ce(OH)3 nanoparticles were as small as 2 nm. The nanoparticles were fitted into the tiny aqueous channels of the liquid crystal matrix, which presented a Pn3m space group. X-ray absorption near edge structure measurements were used to determine the Ce(iii) fraction of the proenzyme-like nanoparticles, which was around 85%. The Ce(iii) fraction dramatically dropped to around 5% after contact with H2O2 because of the conversion of Ce(OH)3 to CeO(2-x) nanoparticles. The CeO(2-x) nanoparticles showed superoxide dismutase-like activity in contrast to the inactive Ce(OH)3 form. The proof of concept presented in this work opens up new possibilities for using nanoparticles as artificial proenzymes that are activated by a biochemical trigger in vivo.

Confined naked gold nanoparticles in ionic liquid films.

Surface-clean Au nanoparticles (NPs) confined in films of ionic liquids (ILs) can be easily fabricated by sputtering deposition. A silicon wafer coated with films of both hydrophobic (bis((trifluoromethyl)sulfonyl)amide, NTf2-) and hydrophilic (tetrafluoroborate, BF4-) imidazolium-based ILs forms an 'ionic carpet-like' structure that can be easily decorated with Au NPs of 5.1 and 6.5 nm mean diameter, respectively. The depth profile distribution of the Au NPs depends on the arrangement of the IL, which is controlled mainly by the anion volume. Higher concentrations of Au NPs are found closer to the IL surface for the system containing a larger anion (NTf2) whereas Au NPs are located deeper in the IL for the system containing a smaller anion (BF4). The Au NPs are well distributed over the IL/Si support and are strictly confined in a single layer of the IL. This method is among the most simple and versatile for the generation of liquid layers containing surface-clean, stable and confined Au NPs.

Straightforward synthesis of bimetallic Co/Pt nanoparticles in ionic liquid: atomic rearrangement driven by reduction-sulfidation processes and Fischer-Tropsch catalysis.

Unsupported bimetallic Co/Pt nanoparticles (NPs) of 4.4 ± 1.9 nm can be easily obtained by a simple reaction of [bis(cylopentadienyl)cobalt(ii)] and [tris(dibenzylideneacetone) bisplatinum(0)] complexes in 1-n-butyl-3-methylimidazolium hexafluorophosphate IL at 150 °C under hydrogen (10 bar) for 24 h. These bimetallic NPs display core-shell like structures in which mainly Pt composes the external shell and its concentration decreases in the inner-shells (CoPt3@Pt-like structure). XPS and EXAFS analyses show the restructuration of the metal composition at the NP surface when they are subjected to hydrogen and posterior H2S sulfidation, thus inducing the migration of Co atoms to the external shells of the bimetallic NPs. Furthermore, the isolated bimetallic NPs are active catalysts for the Fischer-Tropsch synthesis, with selectivity for naphtha products.