Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.

Excitation energies from ground-state density-functionals by means of generator coordinates

The generator-coordinate method is a flexible and powerful reformulation of the variational principle. Here we show that by introducing a generator coordinate in the Kohn-Sham equation of density-functional theory, excitation energies can be obtained from ground-state density functionals. As a viability test, the method is applied to ground-state energies and various types of excited-state energies of atoms and ions from the He and the Li isoelectronic series. Results are compared to a variety of alternative DFT-based approaches to excited states, in particular time-dependent density-functional theory with exact and approximate potentials.

Sodium piperidine-1-carbodithioate dihydrate

The asymmetric unit of the title compound, Na(+)center dot C(6)H(10)NS(2) center dot 2H(2)O, is composed of a sodium cation, a piperidinedithiocarbamate anion which exhibits positional disorder, and two lattice water molecules. The atoms of the piperidine ring are divided over two sites with occupancy factors of 0.554 (6) and 0.446 (6). In the crystal, the sodium cation (coordination number of 6) and the piperidinedithiocarbamate anion are linked, forming an infinite two-dimensional network extending parallel to (001). O-H center dot center dot center dot S hydrogen bonds, involving the lattice water molecules, also aid in stabilizing the crystal sructure.

2-Bromo-2-methyl-N-p-tolylpropanamide

In the title molecule, C(11)H(14)BrNO, there is twist between the mean plane of the amide group and the benzene ring [C(=O)-N-C...;C torsion angle = -31.2 (5)degrees]. In the crystal, intermolecular N-H...O and weak C-H...O hydrogen bonds link molecules into chains along [100]. The methyl group H atoms are disordered over two sets of sites with equal occupancy.

Ammonium piperidine-1-carbodithioate

The title compound, NH(4) +center dot C(6)H(10)NS(2) -, is composed of an ammonium cation and a piperidine-1-carbodithioate anion which exhibits positional disorder. The atoms of the ring have a structural disorder and they are divided into two sites, with occupancy factors of 0.584 and 0.426.. In the crystal, the cation and anion are linked by N-H...S hydrogen bonds to form an infinite two-dimensional network.

Bulk structures of PtO and PtO(2) from density functional calculations

Platinum plays an important role in catalysis and electrochemistry, and it is known that the direct interaction of oxygen with Pt surfaces can lead to the formation of platinum oxides (PtO(x)), which can affect the reactivity. To contribute to the atomistic understanding of the atomic structure of PtO(x), we report a density functional theory study of the atomic structure of bulk PtO(x) (1 <= x <= 2). From our calculations, we identified a lowest-energy structure (GeS type, space group Pnma) for PtO, which is 0.181 eV lower in energy than the structure suggested by W. J. Moore and L. Pauling [J. Am. Chem. Soc. 63, 1392 (1941)] (PtS type). Furthermore, two atomic structures were identified for PtO(2), which are almost degenerate in energy with the lowest-energy structure reported so far for PtO(2) (CaCl(2) type). Based on our results and analysis, we suggest that Pt and O atoms tend to form octahedron motifs in PtO(x) even at lower O composition by the formation of Pt-Pt bonds.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.

Lignin phenols used to infer organic matter sources to Sepetiba Bay - RJ, Brasil

Lignin phenols were measured in the sediments of Sepitiba Bay, Rio de Janeiro, Brazil and in bedload sediments and suspended sediments of the four major fluvial inputs to the bay: Sao Francisco and Guandu Channels and the Guarda and Cacao Rivers. Fluvial suspended lignin yields (Sigma 8 3.5-14.6 mgC 10 g dw(-1)) vary little between the wet and dry seasons and are poorly correlated with fluvial chlorophyll concentrations (0.8-50.2 mu gC L(-1)). Despite current land use practices that favor grassland agriculture or industrial uses, fluvial lignin compositions are dominated by a degraded leaf-sourced material. The exception is the Guarda River, which has a slight influence from grasses. The Lignin Phenol Vegetation Index, coupled with acid/aldehyde and 3.5 Db/V ratios, indicate that degraded leaf-derived phenols are also the primary preserved lignin component in the bay. The presence of fringe Typha sp. and Spartina sp. grass beds surrounding portions of the Bay are not reflected in the lignin signature. Instead, lignin entering the bay appears to reflect the erosion of soils containing a degraded signature from the former Atlantic rain forest that once dominated the watershed, instead of containing a significant signature derived from current agricultural uses. A three-component mixing model using the LPVI, atomic N:C ratios, and stable carbon isotopes (which range between -26.8 and -21.8 parts per thousand) supports the hypothesis that fluvial inputs to the bay are dominated by planktonic matter (78% of the input), with lignin dominated by leaf (14% of the input) over grass (6%). Sediments are composed of a roughly 50-50 mixture of autochthonous material and terrigenous material, with lignin being primarily sourced from leaf. (C) 2010 Elsevier Ltd. All rights reserved.

DFT and electrochemical studies on nortriptyline oxidation sites

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule`s activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

Characterization and greenhouse evaluation of Brazilian calcined nonapatite phosphate rocks for rice

Little information is available on the agronomic effectiveness of calcined nonapatite phosphate rock (PR) sources containing crandallite minerals in the form of Ca-Fe-Al-P for flooded and upland rice (Oryza sativa L.). We conducted laboratory and greenhouse studies to (i) characterize the mineralogical composition, (ii) investigate the solubility and dissolution behavior, and (iii) evaluate the agronomic effectiveness of two nonapatite PR sources (Juquia and Sapucaia) from Brazil and compared them with (i) a highly reactive Gafsa PR (Tunisia) containing apatite in the form of Ca-P and (ii) a reference water-soluble triple superphosphate (TSP) for flooded and upland rice. After calcination at 500 degrees C for 4 h, the solubility of Juquia PR and Sapucaia PR in neutral ammonium citrate (NAC) significantly increased from almost nil to a maximum of 39.3 and 114 g P kg(-1), respectively. X-ray diffraction showed that crystalline crandallite mineral was transformed to an amophorus form after calcination. The solubility behavior of the two calcined PR sources followed the same trend as Gafsa PR, that is, P release decreased with increasing equilibrium pH in the 0.01 M KCl solution (PH 3.0-8.0). At PH 3, the solubility followed: Gafsa PR > calcined Sapucaia PR > calcined Juquia PR. No P release was detected from any of the PR sources at pH >= 5.0 in the solution, indicating the Ca-P characteristic of the Ca-Fe-Al-P mineral controlled P dissolution of the calcined PR. Without calcination, both Juquia PR and Sapucaia PR were totally ineffective for upland rice grown on a Hiwassee clay loam (fine, kaolinitic, thermic Rhodic Kanhapludult) with pH 5.4 whereas a significant P response was observed with the calcined PR samples. For flooded rice grown on Hiwassee soil, the calcined Juquia PR and Sapucaia PR were 66 and 72%, respectively, as effective as TSP in increasing rice grain yield whereas Gafsa PR was ineffective. For upland rice grown on the unlimed soil, Gafsa PR was as effective as TSP in increasing rice grain yield whereas calcined Juquia PR and Sapucaia PR were 89 and 83% of TSP. The effectiveness of Gafsa PR was reduced to 0% after the soil was limed to pH 7.0 whereas the two calcined PR sources were reduced to 49% of TSP. Soil available P extracted by iron oxide impregnated filter paper (Pi test) or anion-exchange resin after rice harvest correlated well with P uptake by rice grain for flooded and upland rice.

Agronomic evaluation of calcined crandallite from three Brazilian phosphate deposits

Samples from the weathering mantle containing crandallite of three Brazilian phosphate deposits, Tapira, Catalo, and Juqui, were characterized, calcined, and agronomically evaluated. The calcination process increased total phosphorus (P) and neutral ammonium citrate soluble (NAC) P contents of all samples. The NAC solubility of original Tapira, Catalo, and Juqui was about 5% of total P, whereas for calcined samples it was 54, 16, and 53%, respectively. In a greenhouse study, rates of P were applied at 0, 10, 20, 40, 80, and 120mg P kg(-1) from the calcined materials and MCP (monocalcium phosphate) to an Ultisol cropped with upland and flooded rice for 65 days. The results showed that the calcined P samples increased dry-matter yield and P uptake with increasing rates of P applied for both crops. Tapira and Juqui were more effective for flooded than for upland rice. The calculated values of relative agronomic effectiveness of Tapira, Catalo, and Juqui with respect to MCP were 57, 48, and 53% in dry-matter yield for upland rice and 64, 50, and 69% for flooded rice, respectively.

Successful maintenance of a stingless bee population despite a severe genetic bottleneck

Stingless bees play an important ecological role as pollinators of many wild plant species in the tropics and have significant potential for the pollination of agricultural crops. Nevertheless, conservation efforts as well as commercial breeding programmes require better guidelines on the amount of genetic variation that is needed to maintain viable populations. In this context, we carried out a long-term genetic study on the stingless bee Melipona scutellaris to evaluate the population viability consequences of prolonged breeding from a small number of founder colonies. In particular, it was artificially imposed a genetic bottleneck by setting up a population starting from only two founder colonies, and continued breeding from it for a period of over 10 years in a location outside its natural area of occurrence. We show that despite a great reduction in the number of alleles present at both neutral microsatellite loci and the sex-determining locus relative to its natural source population, and an increased frequency in the production of sterile diploid males, the genetically impoverished population could be successfully bred and maintained for at least 10 years. This shows that in stingless bees, breeding from a small stock of colonies may have less severe consequences than previously suspected. In addition, we provide a simulation model to determine the number of colonies that are needed to maintain a certain number of sex alleles in a population, thereby providing useful guidelines for stingless bee breeding and conservation efforts.

Effect of bioglass additions on the sintering of Y-TZP bioceramics

The objective of this work was to evaluate the influence of bioglass additions on the sintering and mechanical properties of yttria-stabilized zirconia ceramics, Y-TZP Samples containing different bioglass additions, varying between 0 and 30 wt.%, were cold uniaxial pressed at 80 MPa and sintered in air at 1200 degrees C or 1300 degrees C for 120 min. Sintered samples were characterized by X-ray Diffractometry and Scanning Electron Microscopy. Hardness and fracture toughness were determined using Vickers indentation method. As a preliminary biological evaluation, in vitro cytotoxicity tests by Neutral Red Uptake method (using mouse connective tissue cells, NCTC clone L929 from ATCC bank) were realized to determine the cytotoxicity level of ZrO(2)-bioglass ceramics. The increasing of bioglass amount leads to the decreasing of relative density due to martensitic (tetragonal-monoclinic) transformation during cooling of the sintered samples. Y-TZP samples sintered at 1300 degrees C containing 5 wt.% of bioglass presented the best results. with high relative density, hardness and fracture toughness of 11.3 GPa and 6.1 MPa m(1/2), respectively. Furthermore, the un-cytotoxic behavior was observed in all sintering conditions and bioglass amounts used in this study. (C) 2009 Elsevier B.V. All rights reserved.

Mechanical properties and cytotoxicity of 3Y-TZP bioceramics reinforced with Al(2)O(3) particles

The influence of Al(2)O(3) addition and sintering parameters on the mechanical properties and cytotoxicity of tetragonal ZrO(2)-3 mol% Y(2)O(3) ceramics was evaluated. Samples containing 0, 10, 20 and 30 wt.% of Al(2)O(3) particles were prepared by cold uniaxial pressing (80 MPa) and sintered in air at 1500, 1550 and 1600 degrees C for 120 min. The effects of the sintering conditions on the microstructure were analyzed by X-ray diffraction analysis and scanning electron microscopy. Hardness and fracture toughness were determined by the Vickers indentation method and the mechanical resistance by four-point bending tests. As a preliminary biological evaluation, ""in vitro"" cytotoxicity tests were realized to determine the cytotoxic level of the ZrO(2)-Al(2)O(3) composites, using the neutral red uptake method with NCTC clones L929 from the American Type Culture Collection (ATCC) bank. Fully dense ceramic materials were obtained with a hardness ranging between 1340 HV and 1585 HV, depending on the amount of Al(2)O(3) in the ZrO(2) matrix. On the other hand, no significant influence of the Al(2)O(3) addition on fracture toughness was observed, exhibiting values near 8 MPa m(1/2) for all compositions and sintering conditions studied. The non-cytotoxic behavior, the elevated fracture toughness, the good bending strength (sigma(f) = 690 MPa) and the elevated Weibull`s modulus (m = 11) exhibited by the material, show that these ceramic composites are highly suitable biomaterials for dental implant applications. (C) 2008 Elsevier Ltd and Techna Group S.r.l. All rights reserved.