Activation of electrode surfaces: semiquantitative characterization of electrode surfaces modified with heteropolyanions

Several Techniques have been used successively or in combination to approach a better understanding of surfaces modified by silicotungstic heteropolyanion. Due to the strikingly high activity of these electrodes for the hydrogen evolution reaction, in particular, there exists a need to identify the chemical composition of the catalyst, to evaluate the amount of catalyst on the surface, and to study the electrochemical behaviour of the “catalyst” itself. Plasma emission spectrometry shows semi-quantitatively that the catalyst resembles the starting material closely, although it is not possible at present to give the exact chemical formula. Electron microprobe analysis (EMA) confirms the presence of tungsten, and especially silicon, on the surface, even though the concentration of this last element is very low. The absence of platinum in the starting HPA, as well as on the electrode surface, is also clearly demonstrated by EMA, which is of prime importance in showing that the “HPA catalyst” is active by itself. Combined coulometry and UV-visible spectroscopy have been used to evaluate the amount of HPA consumed during electrolysis. Cyclic voltammetry shows a surface redox couple corresponding to the catalyst, and well separated from the first redox couple of SiW₁₂O^4-₄ in 0.5 M H₂SO₄ solution. A better understanding of the activation-deactivation processes of the catalytic electrode surface ensues.     

Prebiotic chemistry: A fuzzy field

If prebiotic chemistry is defined as the study of the chemical steps, which lead to the first organisms, a clear-cut definition of “living organism” is needed. Unfortunately, no unambiguous and universally accepted definition exists for the concept “living”. Under these conditions, fuzzy logic is probably the methodological tool that can best be used to handle questions pertaining to “the origin of life”. A conventional scale must, however, be defined which interestingly enough, depends necessarily on our present-day scientific knowledge.     

An infrared spectroscopic study of hydrogen bonding in ethyl phenol: A model system for polymer phenolics

A detailed analysis of the bands appearing in the OH stretching region of the infrared spectrum of ethyl phenol solutions is presented. In cyclohexane solutions, the band due to “free” (non-hydrogen-bonded groups) contains overlapping contributions from both monomeric and end-group species. Other assignments are made on the basis of whether the proton and oxygen in a particular OH group are both involved in hydrogen bonds (as “donors” and “acceptors”, respectively), or if only the proton is acting as a donor. The strongest band in the spectra obtained at the highest concentration of ethyl phenol is due to OH groups present in linear chains of hydrogen-bonded OH groups (as recognized in numerous other studies), but a band due to cyclic trimers has also been identified. The assignment of other modes is more uncertain and various possibilities are discussed. In toluene solutions, assignments are more complicated, because bands due to OH–π hydrogen bonds are observed instead of free groups. Finally, the data from cyclohexane solutions was used to calculate equilibrium constants capable of describing the distribution of species present. A new methodology for determining the equilibrium constant describing association in the form of dimers is described.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

Adsorption of NOM onto Activated Carbon: Effect of Surface Charge, Ionic Strength, and Pore Volume Distribution

Adsorption of natural organic matter (NOM) onto seven activated carbons with a wide range of surface properties was studied at high and low ionic strength over a range of pH values. From adsorption isotherm studies it was found that, for six of seven carbons, at low surface concentrations, increased ionic strength decreased NOM adsorption. As the surface concentration increased, the adsorption isotherms converged and intersected, after which the addition of salt resulted in increased adsorption. This “crossover point” marked a change in the adsorption mechanism from the “screening reduced” to the “screening enhanced” adsorption regimes. The adsorption mechanisms are extremely complicated and appear attributable to various factors, including electrostatic forces, pore volume distribution, and chemical interactions between the NOM and the surface functionalities on the carbon surfaces.     

Metal Nanoparticles on Polymer Surfaces: 5. Catalytic Activity of Colloidal Platinum Films Incorporated in Polystyrene Surface Layer

The fundamental possibility to enlarge Pt nanoparticles in monolayer ensembles formed on polystyrene surfaces by the adsorption from hydrosol in solution of isopropanol and K₂PtCl₄ is demonstrated for the first time. The enlargement of “seeding” nanoparticles is performed after their preliminary incorporation (partial embedding) into the polymer surface layer by the annealing of a system within the range between “surface” and “bulk” glass transition temperatures of polystyrene. It is shown that a colloidal film of metallic platinum with a thickness up to 200 nm is formed in the course of enlargement and it is mechanically fixed in the polymer surface layer. Such a system exhibits, over a long time, high catalytic activity in the model reaction of methyl viologen reduction with hydrogen.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 398–403.Original Russian Text Copyright © 2005 by Rudoy, Sukhov, Dement’eva, Abkhalimov, Vereshchagina, Kartseva, Ershov.     

A thermodynamic interpretation of the behavior of higher fatty alcohols and acids upon the chromatographic paper

An idea was presented of treating the chromatographed substance as a “solute,” and the chromatographic system, composed of the stationary and the mobile phase as a “solvent.” Moreover the concept of “local equilibrium” was introduced, allowing to regard a given chromatographic spot as a “binary solution.” Thus a possibility arose to apply the classical thermodynamic approach, normally used for binary solutions, and namely: μ_i = μ_i + RT ln x_iƒ_i, where μ_i—chemical potential of the “i”-th compound in the solution, μ_i—chemical potential of the pure “i”-th compound, x_i-molar fraction of the “i”-th compound, ƒ_i—its activity coefficient, in a modified form, suitable for the chromatographic purpose.     

[FeFe]‐Hydrogenase with Chalcogenide Substitutions at the H‐Cluster Maintains Full H2 Evolution Activity

The [FeFe]‐hydrogenase HYDA1 from Chlamydomonas reinhardtii is particularly amenable to biochemical and biophysical characterization because the H‐cluster in the active site is the only inorganic cofactor present. Herein, we present the complete chemical incorporation of the H‐cluster into the HYDA1‐apoprotein scaffold and, furthermore, the successful replacement of sulfur in the native [4Fe_H] cluster with selenium. The crystal structure of the reconstituted pre‐mature HYDA1[4Fe4Se]_H protein was determined, and a catalytically intact artificial H‐cluster variant was generated upon in vitro maturation. Full hydrogen evolution activity as well as native‐like composition and behavior of the redesigned enzyme were verified through kinetic assays, FTIR spectroscopy, and X‐ray structure analysis. These findings reveal that even a bioinorganic active site with exceptional complexity can exhibit a surprising level of compositional plasticity.     

Epithermal neutron flux characterization of the IEA-R1 research reactor,Sao Paulo,Brazil

Summary The nonideality of the epithermal neutron flux distribution at a reactor site parameter (α) and the thermal-to-epithermal neutron ratio (ƒ) were determined in three typical irradiation positions of the IEA-R1 reactor of IPEN-CNEN/SP, Sao Paulo, Brazil, using the “Cd-ratio for multimonitor” and “bare bi-isotopic monitor” methods, respectively. This characterization is to be used in the k₀-method of NAA, recently introduced at the IPEN.     

DFT and ab initio potential energy scan and hydrogen bond analysis of N-substituted hydrazino acetamides: Characterization of the “hydrazinoturn” hydrogen bonding pattern

We studied a series of model primary amides in gas phase at the DFT (B3LYP) and HF at 6-31+G/6-31+G** levels of theory in order to shed light on their conformation, structure, and intramolecular hydrogen bonding network. A potential energy scan was performed by rotating around the appropriate bond for each molecule studied in this paper. In this manner, it was possible to show that the amidic group of these model compounds acts as H-bond donor and interacts with two different H-bond acceptors which stabilizes a C₈ pseudocycle, the so called “hydrazinoturn”. This study was addressed theoretically in order to understand the conformation adopted by hydrazino acetamides as model compounds for aza-β³-peptides. We thus investigated the conformational analysis of hydrazinoturns computationally and showed that these systems represent a very stabilizing folding driving force, provided that the neighboring molecular functional groups do not imply other competing hydrogen bonding patterns.     

Individuation of characteristic parameters of “glass paste” of Meridional Etruria by the use of scientific methodologies

The individuation of parameters that characterize decorations in “glass paste” of Etruscan jewels in Meridional Etruria area, by the use of scientific methodologies, has the aim to collocate this typology of manufacts in a historical and geographical context and to improve the knowledge of the technology connected with their realization. The term “glass paste” is widely used in humanistic literature to describe different materials, all based on a “glass like” composition, but its definition is lacking or confusing if the term is not referred to a scientific meaning.The glass analysis is difficult owing to the complexity of the elements that compose the various classes of vitreous materials. For this reason the interpretation of the composition table containing the values of the numerous glass elements, induces the use of statistical methods for the elaboration of the results. The multivariate analysis can be a valid tool for an immediate lecture of the common characteristics of the different typologies of vitreous materials.In this work, the application of the Principal Component Analysis (PCA), has been applied for the elaboration of chemical composition data obtained by electronic microanalysis (SEM-EDS) on findings coming from Etruscan archaeological sites of Nepi and Cerveteri, and on pearls of a necklace from Castellani's Collection. Besides, an attempt has been made to compare the chemical elements found in the vitreous materials of the jewelry with the elements of sands from probable sites along the rivers present in the Etruscan sites by following the indications reported by historical fonts.The obtained results furnished information in various directions, either for the characterization of each historical sample analyzed or the validation of the applied statistical methodology for the composition data elaboration, besides it has been possible to contribute in the knowledge of the possible existence of glass production sites in the Meridional Etruria, more specifically for the realization of decoration in glass paste.     

Biofuel cell controlled by enzyme logic network — Approaching physiologically regulated devices

A “smart” biofuel cell switchable ON and OFF upon application of several chemical signals processed by an enzyme logic network was designed. The biocomputing system performing logic operations on the input signals was composed of four enzymes: alcohol dehydrogenase (ADH), amyloglucosidase (AGS), invertase (INV) and glucose dehydrogenase (GDH). These enzymes were activated by different combinations of chemical input signals: NADH, acetaldehyde, maltose and sucrose. The sequence of biochemical reactions catalyzed by the enzymes models a logic network composed of concatenated AND/OR gates. Upon application of specific “successful” patterns of the chemical input signals, the cascade of biochemical reactions resulted in the formation of gluconic acid, thus producing acidic pH in the solution. This resulted in the activation of a pH-sensitive redox-polymer-modified cathode in the biofuel cell, thus, switching ON the entire cell and dramatically increasing its power output. Application of another chemical signal (urea in the presence of urease) resulted in the return to the initial neutral pH value, when the O₂-reducing cathode and the entire cell are in the mute state. The reversible activation–inactivation of the biofuel cell was controlled by the enzymatic reactions logically processing a number of chemical input signals applied in different combinations. The studied biofuel cell exemplifies a new kind of bioelectronic device where the bioelectronic function is controlled by a biocomputing system. Such devices will provide a new dimension in bioelectronics and biocomputing benefiting from the integration of both concepts.     

Production of valuable hydrocarbons by catalytic degradation of a mixture of post-consumer plastic waste in a fluidized-bed reactor

A mixture of post-consumer plastic waste (PE/PP/PS/PVC) was pyrolyzed over various catalysts using a fluid catalytic cracking (FCC) process operating isothermally at ambient pressure. Experiments with various catalysts gave good yields of valuable hydrocarbons with differing selectivity in the final products dependent on reaction conditions. A model based on kinetic and mechanistic schemes for the observed products associated with chemical reactions and catalyst deactivation has been developed. The model gives a good representation of experimental results. It is also an improvement on the currently available empirical “lumping” techniques which are usually severely restricted in terms of product definitions. Additionally, this model represents the benefits of product selectivity for the chemical composition in relation to the effect of structurally different catalyst types, and the performance of the reaction temperature used as well as the particle size of the catalyst selected.     

A tensiometric study of diamond (111) and (110) faces

Tensiometric contact angle measurements of diamond surfaces in both the air:water and octane:water systems reveal moderate hydrophobicity, as might be expected of a surface with a minority of oxygen-containing groups. High-temperature reaction with oxygen or hydrogen leads to large changes in the contact angles. Spectroscopic methods show a “one-third” coverage by oxygen. The response to pH and adsorption of ferric ion suggests that the oxygen is present as an hydroxyl group. Steric resistance to higher oxide coverage, because of the small lattice constant of the crystal, may be an explanation for the natural hydrophobicity of the diamond surface.     

Carbon,nitrogen, and oxygen hypercoordination in half-sandwich and sandwich structures

The structures and stabilities of a number of neutral and charged half-sandwich (pyramidal) and sandwich compounds, which obey the “electron octet” rule and contain hypercoordinate carbon, nitrogen, and oxygen atoms, were studied by ab initio MP2(full)/6-311+G** and density functional B3LYP/6-311+G** methods. Introduction of lithium counterions or bridging hydrogen atoms can provide an additional stabilization of non-classical systems with hypercoordinate centers.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 527–540, March, 2005.     

Indoor measurements of microclimate variables and ozone in the church of San Vincenzo (Monastery of Bassano Romano — Italy): A pilot study

This experiment describes a way of operation in MMA-CH, Microclimate Multivariate Analysis for Cultural Heritage. It is realised by choosing appropriate meteorological and air composition parameters according to the environment to be investigated, measuring them by appropriate instruments and making acquisition of time series to find out all possible correlations. It is possible to understand how this branch of multivariate analysis could contribute to the “science of conservation” by applying an appropriate microclimatic and air composition monitoring and processing. Microclimate parameters such us air temperature, relative humidity, mixing ratio and air composition parameters such as tropospheric ozone content were monitored during a summer period to assess their impact on the cultural heritage of the Benedictine Monastery dedicated to San Vincenzo Martire (Diocletian's Christians persecution). This marvellous place is settled next to Bassano Romano village, in the Sabatini mountains rural area. The importance of the site is established by the presence of many art treasures, like 2 frescos of '700, 2 frescos of '600 (Caravaggio School) and by a marble statue of Jesus (“The Jesus cross carrying”) which is recently attributed to Michelangelo as the original one.     

Amine groups functionalized gel-type resin supported Pd catalysts: Physicochemical and catalytic properties in hydrogenation of alkynes

Palladium catalysts (0.125–0.5 wt.% Pd) supported by amine groups—functionalized gel-type resin (FCN) were studied in the hydrogenation of alkynes reagents, 2-butyne-1,4-diol and phenylacetylene. The catalysts were prepared by two routes. The first, “OAc” is based on the immobilization of Pd-precursor in the pre-swollen resin from THF solution of Pd(OAc)₂, followed by chemical reduction of the Pd-centers. This method produces Pd particles of size in nano-scale. The second procedure, “aq” implies the deposition of Pd-species on dry resin beads using aqueous solution of PdCl₂. Reduction of these Pd-species gives relatively large Pd particles, dominating are 30–50 nm in size. The SEM studies performed over the cross-section of catalysts grains showed location of Pd in outer shell of polymer beads in both “OAc” and “aq” catalysts; however, thinner layer of Pd appears in “aq” series catalysts. In the presence of all catalysts, prepared by “OAc” and “aq” methods the selectivity towards alkenes is high, above 90%. The catalysts of “aq’ series are much more active and more selective than “OAc” analogues giving selectivity to alkene ca. 94% at almost complete conversion of alkynes. Moreover, catalytic performance of “aq’ series catalyst is unchanged under recycling use. The catalyst was recovered and reused 4 times, maintaining its catalytic efficiency.     

Nanocrystal conversion chemistry: A unified and materials-general strategy for the template-based synthesis of nanocrystalline solids

The concept of nanocrystal conversion chemistry, which involves the use of pre-formed nanoparticles as templates for chemical transformation into derivative solids, has emerged as a powerful approach for designing the synthesis of complex nanocrystalline solids. The general strategy exploits established synthetic capabilities in simple nanocrystal systems and uses these nanocrystals as templates that help to define the composition, crystal structure, and morphology of product nanocrystals. This article highlights key examples of “conversion chemistry” approaches to the synthesis of nanocrystalline solids using a variety of techniques, including galvanic replacement, diffusion, oxidation, and ion exchange. The discussion is organized according to classes of solids, highlighting the diverse target systems that are accessible using similar chemical concepts: metals, oxides, chalcogenides, phosphides, alloys, intermetallic compounds, sulfides, and nitrides.     

Voltammetric and radioactive labeling studies of single crystal and polycrystalline rhodium electrodes in sulfate-containing electrolytes

Adsorption of sulfate/bisulfate anions on single crystal Rh(111) (ordered/disordered) and polycrystalline rhodium electrodes in perchloric acid solution was studied by the use of cyclic voltammetry and the radioactive labeling method. The ordered Rh(111) surface was characterized by LEED and Auger spectroscopy to verify its well-defined character. Details of the surface chemistry of the anions interacting with the three rhodium substrates are different. This is considered as evidence that a long-range order of the metal electrodes alters the structure of chemisorbed hydrogen and oxygen significantly and that this structure is affected by the reversibly interacting species. Likewise, the adsorbed layer of sulfate anions on Rh(111) is more stable than that on other rhodium surfaces due to a favorable spatial configuration of the anions and surface water molecule network, which are proposed to be cross linked by hydrogen bonding. Overall, the adsorption reversibility of sulfate was confirmed with respect to the bulk concentration of the adsorbate and the electrode potential (provided that the surface oxidation is avoided). Radiochemical data reveal that, in the studied bulk concentration range (up to about 10⁻³ M), the uptake of anions by Rh(111) is limited to ca. 40% of the theoretical maximum coverage. The interaction of sulfate with Pt(111), and corresponding voltammetry in perchloric acid electrolyte are also brought into focus. It is concluded that only a part of the Pt(111) “butterfly” can be accounted for by adsorption of high energy hydrogen. No high energy hydrogen has been found to exist on Rh(111), as inferred earlier in our laboratory.     

On the ionic conductivity and phase transitions in the Li2SO4---Li2WO4 system and their relation to ion transport mechanism

Secco et al. have performed several measurements of ionic conductivity, which they have considered as “convincing evidence” that the “paddle-wheel” mechanism does not contribute significantly to ion conductivity in Li₂SO₄-based compositions. However, a comparison of their results in the high-conductivity range with those of other investigators suggests that their data are artifacts. The cause of this is that the resistance of their sulfate-rich samples is about 0.1 ohm at high temperatures. Thus, their results are reliable only for “normal,” i.e., low, conductivities. It is briefly summarized why the “paddle-wheel” mechanism for ion transport is superior to a percolation-type mechanism for a few high-conducting phases.