Effect of ionic conductivity of a PAN–PC–LiClO<Subscript>4</Subscript> solid polymeric electrolyte on the performance of a TiO<Subscript>2</Subscript> photoelectrochemical cell

A nanoparticle TiO₂ solid-state photoelectrochemical cell has been fabricated. The effect of ionic conductivity of a solid electrolyte of polyacrylonitrile (PAN)–propylene carbonate (PC)–lithium perchlorate (LiClO₄) on the performance of a photoelectrochemical cell of indium tin oxide (ITO)/TiO₂/PAN–PC–LiClO₄/graphite has been investigated. A nanoparticle TiO₂ film was deposited onto ITO-covered glass substrate by controlled hydrolysis technique. A solid electrolyte of PAN–LiClO₄ with PC plasticizer prepared by solution casting technique was used as a redox couple medium. The room temperature conductivity of the electrolyte was determined by AC impedance spectroscopy technique. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows a photovoltaic effect under illumination. The short-circuit current density, J _sc, and open-circuit voltage, V _oc, vary with the conductivity of the electrolyte. The highest J _sc of 2.82 μA cm⁻² and V _oc of 0.56 V were obtained at the conductivity of 4.2 × 10⁻⁴ Scm⁻¹ and at the intensity of 100 mW cm⁻².     

Hydrogenation of a Magnesium–Mg<Subscript>2</Subscript>Yb Alloy

A possibility for hydrogenation of a two-phase magnesium alloy containing intermetallic compound Mg₂Yb by hydrogen and ammonia is found to yield hydride phases MgH₂ and MgYbH_3.5 in various temperature schedules. The use of ammonia in the range 350–500°C leads to the formation of magnesium and ytterbium nitrides.     

TiO<Subscript>2</Subscript>-assisted photodegradation of pharmaceuticals — a review

Pharmaceutical compounds have been detected in the environment and potentially arise from the discharge of excreted and improperly disposed medication from sewage treatment facilities. In order to minimize environmental exposure of pharmaceutical residues, a potential technique to remove pharmaceuticals from water is the use of an advanced oxidation process (AOP) involving titanium dioxide (TiO₂) photocatalysis. To evaluate the extent UV/TiO₂ processes have been studied for pharmaceutical degradation, a literature search using the keywords ‘titanium dioxide’, ‘photocatalysis’, ‘advanced oxidation processes’, ‘pharmaceuticals’ and ‘degradation’ were used in the ISI Web of Knowledge TM, Scopus TM and ScienceDirect TM databases up to and including articles published on 23 November 2011. The degradation rates of pharmaceuticals under UV/TiO₂ treatment were dependent on type and amount of TiO₂ loading, pharmaceutical concentration, the presence of electron acceptors and pH. Complete mineralization under particular experimental conditions were reported for some pharmaceuticals; however, some experiments reported evolution of toxic intermediates during the photocatalytic process. It is concluded that the UV/TiO₂ system is potentially a feasible wastewater treatment process, but careful consideration of the treatment time, the loading and the type of TiO₂ (doped vs. undoped) used for a particular pharmaceutical is necessary for a successful application (198 words).      

Is the μ‐Oxo‐μ‐Peroxodiiron Intermediate of a Ribonucleotide Reductase Biomimetic a Possible Oxidant of Epoxidation Reactions?

Density functional calculations on a mu-oxo-mu-peroxodiiron complex (1) with a tetrapodal ligand BPP (BPP=N,N-bis(2-pyridylmethyl)-3-aminopropionate) are presented that is a biomimetic of the active site region of ribonucleotide reductase (RNR). We have studied all low-lying electronic states and show that it has close-lying broken-shell singlet and undecaplet (S=0, 5) ground states with essentially two sextet spin iron atoms. In strongly distorted electronic systems in which the two iron atoms have different spin states, the peroxo group moves considerably out of the plane of the mu-oxodiiron group due to orbital rearrangements. The calculated absorption spectra of (1,11)1 are in good agreement with experimental studies on biomimetics and RNR enzyme systems. Moreover, vibrational shifts in the spectrum due to (18)O(2) substitution of the oxygen atoms in the peroxo group follow similar trends as experimental observations. To identify whether the mu-oxo-mu-1,2-peroxodiiron or the mu-oxo-mu-1,1-peroxodiiron complexes are able to epoxidize substrates, we studied the reactivity patterns versus propene. Generally, the reactions are stepwise via radical intermediates and proceed by two-state reactivity patterns on competing singlet and undecaplet spin state surfaces. However, both the mu-oxo-mu-1,2-peroxodiiron and mu-oxo-mu-1,1-peroxodiiron complex are sluggish oxidants with high epoxidation barriers. The epoxidation barriers for the mu-oxo-mu-1,1-peroxodiiron complex are significantly lower than the ones for the mu-oxo-mu-1,2-peroxodiiron complex but still are too high to be considered for catalytic properties. Thus, theory has ruled out two possible peroxodiiron catalysts as oxidants in RNR enzymes and biomimetics and the quest to find the actual oxidant in the enzyme mechanism continues.     

Analogs of ecdysteroids with a tetrasubstituted Δ<Superscript>8,14</Superscript>-bond

By hydrogenation of (20R,22R)-6α,14α,25-trihydroxy-and (20R,22R)-6β,14α,25-trihydroxy-2,3:20,22-bis(isopropylidenedioxy)-5α-cholest-7-enes on a catalyst (Raney nickel) the corresponding (5α,6α)-and (5β,6β)-epimers of previously unknown Δ^8,14-6-hydroxy derivatives of ecdysteroids were synthesized.     

Measurement of the Rate Constant of a Reaction of Chlorine Atoms with CH<Subscript>3</Subscript>Br in a Temperature Range of 298–358 K Using the Resonance Fluorescence of Chlorine Atoms

The rate constant of the reaction of chlorine atoms with CH₃Br was measured in a temperature range of 298–358 K using the resonance fluorescence of chlorine atoms. The possible role of this reaction in atmospheric chemistry and fire extinguishing was discussed. It was found that this reaction is homogeneous in contrast to the previously studied reaction of chlorine atoms with CH₃I, with occurs at the reactor surface.     

Formation of the center of ignition in a CH<Subscript>3</Subscript>Cl–Cl<Subscript>2</Subscript> mixture under the action of UV light

The dependence of temperature on time is investigated using a microthermocouple at different distances from a UV light source in a mixture of chlorine and chloromethane. These relationships give an idea of the size and location of a center of photoignition. It is found that if the size of the reaction vessel in the direction of the luminous flux is much greater than the dimensions of the ignition center, the thermal expansion of a reacting gas mixture has a huge impact on such photoignition parameters as the critical concentration limits and the critical intensity of UV radiation. It is found that by increasing the length of the vessel, some chlorinated combustible mixtures lose the ability to ignite when exposed to UV light.     

Preparation of LiTaO<Subscript>3</Subscript> nanoparticles by a sol–gel route

A sol–gel route was developed to prepare pure ultrafine LiTaO₃ powders using Ta₂O₅, Li₂CO₃, citric acid (CA) as chelating agent, ethylene glycol (EG) as esterification agent and polyethylene glycol (PEG) as dispersant. The effects of pH value and heat treatment temperature of powder precursor on the synthesis of LiTaO₃ powders were investigated. The phase content and morphology of the final product were evaluated by XRD, SEM and TEM. A transparent gel was produced when heating a mixed-solution of CA, EG, Li and Ta ions with a molar ratio of [CA]:[EG]:[Li]:[Ta] = 3.0:6.0:1.0:1.0 and 2‰ PEG additions with a pH value of 7 at water bath temperature of 80 °C. The results showed that single phase LiTaO₃ powders with average particle sizes of nanometers were produced after heat treatment of the powder precursor at 650, 700, 800, and 900 °C respectively for 2 h.     

Synthesis,X-ray analysis,and quantum-chemical DFT study of features in formation of a binuclear phenanthroline complex with a V<Superscript>IV</Superscript>–O–V<Superscript>V</Superscript> core

A new mixed-valence complex [(O)(phen)₂V^IV(μ-O)V^V(O)phen)(mal)]⁺ was synthesized and characterized by the X-ray structural analysis. Its geometric structure was simulated by the DFT M06/6-31G(d,p) method. Comparison of calculated and experimental data made it possible to draw a conclusion on the oxobridging nature of the bond between vanadium fragments and to confirm the value of the target compound charge. The energy characteristics of cation formation reactions in solution were estimated. It was found that the oxidation of V^IV to V^V assists subsequent substitution of ligands. Joining [(O)V^IV(phen)₂]²⁺ and [(O)V^V(O)(phen)(mal)]^– particles proceeds by the donor-acceptor mechanism.     

The synthesis of a lanthanum metal–organic framework and its sensitivity electrochemical detection of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A lanthanum metal–organic framework, [La(BTC)(H₂O)(DMF)] (H₃BTC = 1, 3, 5-benzenetricarboxylic acid), was synthesized under mild hydrothermal conditions. The synthesized [La(BTC)(H₂O)(DMF)] was characterized by scanning electron microscopy in combination with energy dispersive X-ray spectroscopy (SEM/EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FT-IR). Its electrochemical properties and electrocatalytic activity towards H₂O₂ reduction in acidic media were studied by cyclic voltammetry (CV) and amperometric current–time response. The [La(BTC)(H₂O)(DMF)] modified electrode shows good electrochemical behavior and performs well electrocatalytic activity towards hydrogen peroxide (H₂O₂) reduction at ca. ?0.7 V. The modified electrode displays a linear range from 5 μM to 2.67 mM and a limit of detection of 0.73 μM to H₂O₂. The [La(BTC)(H₂O)(DMF)] modified electrode also possesses good selectivity and stability. Thus, [La(BTC)(H₂O)(DMF)] will be a promising material for non-enzymatic H₂O₂ sensor.     

Photocatalytic Conversion of a FeCl<Subscript>3</Subscript>–CCl<Subscript>4</Subscript>–ROH System

The photocatalytic transformations of carbon tetrachloride and aliphatic primary alcohols in the presence of iron trichloride and a molar ratio of components FeCl₃: CCl₄: ROH = 1: 300: 2550 were studied. CCl₄ is transformed into chloroform and hexachloroethane after exposure to a mercury lamp (250 W) to the FeCl₃–CCl₄–ROH system at 20°C, whereas the primary ROH alcohols are selectively oxidized into acetals (1,1-dialkoxyalkanes). The maximum conversion of CCl₄ reaches 80%. The kinetics and mechanism of the photocatalytic conversion of the FeCl₃–CCl₄–ROH system are considered.     

Fischer–Tropsch reaction over a Co<Subscript>2</Subscript>-Ni-Mn/SiO<Subscript>2</Subscript> nanocatalyst prepared by thermal decomposition of a new precursor

This study was prepared for the first time the trimetallic nanocatalyst Co₂-Ni-Mn/SiO₂ by thermal decomposition of) [Ni(H₂O)₅Co(dipic)₂].2H₂O + [Mn(H₂O)₅Co(dipic)₂] 2H₂O)/SiO₂, to study the Fischer–Tropsch reaction for conversion of the synthesis gas to light olefins. The catalytic performance of Co₂-Ni-Mn/SiO₂ as a nanocatalyst prepared by thermal decomposition of an inorganic precursor was compared to that of the trimetallic nanocatalysts Co₂-Ni-Mn/SiO₂ as reference nanocatalysts prepared by impregnation and co-precipitation. The characterization of precursor and nanocatalyst were confirmed by thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) specific surface area, and X-ray diffraction (XRD). The Fischer–Tropsch reaction for all nanocatalysts of Co₂-Ni-Mn/SiO₂ was studied at 280–360 °C at a gas hourly space velocity of 3600 h^?1, and a H₂/CO molar ratio of 1:1 at atmospheric pressure. The results showed that the Co₂-Ni-Mn/SiO₂ nanocatalyst prepared by thermal decomposition of an inorganic complex exhibited the higher activity than the other nanocatalysts and showed maximum selectivity to light olefins at 360 °C.     

Phase complex of a NaCl—KCl—SrCl<Subscript>2</Subscript>—Sr(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> four-component system and the physicochemical properties of a eutectic mixture

Tree of phases and crystallization were plotted via a priori prediction, and the coordinates (composition) of a nonvariant point of a NaCl-KCl-SrCl₂-Sr(NO₃)₂ four-component system were determined according to calculations and experimental data. The promise of the method for determining the coordinates of nonvariant points in multicomponent systems was confirmed experimentally. The dependence of density and electroconductivity vs. temperature was studied. The volume dilation of a melt was calculated up to the maximum operating temperature.     

Application of a bismuth film electrode to the voltammetric determination of trace iron using a Fe(III)–TEA–BrO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> catalytic system

A sensitive catalytic voltammetric method for determining trace iron at a bismuth film electrode (BiFE) is described. The method is based on the cathodic reduction of the Fe(III)–triethanolamine (TEA) complex to Fe(II). It has been proved that the addition of KBrO₃ causes rapid oxidation of Fe(II) and TEA, and therefore results in a large increase in the analytical signal from Fe(III) when TEA is placed in alkaline solution. When TEA was present in the solution, operating the BiFE under optimized conditions yielded a stable catalytic voltammetric response for iron, with high sensitivity (0.88 A M^–1), good precision (RSD=3.9%) and a low detection limit (7.7×10^–9 M), obtained without any preconcentration procedure. Possible interferences from the coexisting ions and surface-active substances were investigated. Finally, the method was applied with satisfactory results to the determination of iron in certified reference river water samples.     

Protonation of a Biologically Relevant CuII μ‐Thiolate Complex: Ligand Dissociation or Formation of a Protonated CuI Disulfide Species?

The proton‐induced electron‐transfer reaction of a Cu^II μ‐thiolate complex to a Cu^I‐containing species has been investigated, both experimentally and computationally. The Cu^II μ‐thiolate complex [Cu^II₂( L^MeS )₂]²⁺ is isolated with the new pyridyl‐containing ligand L^MeSSL^Me , which can form both Cu^II thiolate and Cu^I disulfide complexes, depending on the solvent. Both the Cu^II and the Cu^I complexes show reactivity upon addition of protons. The multivalent tetranuclear complex [Cu^I₂Cu^II₂( LS )₂(CH₃CN)₆]⁴⁺ crystallizes after addition of two equivalents of strong acid to a solution containing the μ‐thiolate complex [Cu^II₂( LS )₂]²⁺ and is further analyzed in solution. This study shows that, upon addition of protons to the Cu^II thiolate compound, the ligand dissociates from the copper centers, in contrast to an earlier report describing redox isomerization to a Cu^I disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated Cu^II μ‐thiolate and Cu^I disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [Cu^I(CH₃CN)₄]⁺ and protonated ligand is energetically favored over conversion to a protonated Cu^I disulfide complex.     

Conversion of bio-oxygenates into hydrocarbons in the presence of a commercial Pt–Re/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

It was found that the preliminarily reduced commercial platinum–rhenium catalyst PR-71 exhibited high activity in the conversion of ethanol into C₄–C₁₂ olefins and in the cross-condensation reactions of ethanol with glycerol, acetone, n-propanol, and isopropanol. Acetone and glycerol exhibited the highest reactivity in the cross-condensation reactions; this manifested itself in an increase in the total yield of the target fraction of C₄–C₁₂ hydrocarbons and in a more than 10-fold increase in the yield of products containing the odd numbers of carbon atoms, as compared with the conversion of individual ethanol. The structural studies performed by extended X-ray absorption fine structure (EXAFS) spectroscopy and transmission electron microscopy showed that the high selectivity of PR-71 can be caused by the formation of bimetallic Pt–Re and Pt–Al clusters in the course of the prolonged preliminary reduction of the catalyst.     

Fourier Transform Infrared Spectroscopy and Atomic Force Microscopy Studies of a SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>-Zeolite Matrix for a CuO-CoO Catalyst Prepared by a Sol–Gel Method

Combinations of SiO₂–TiO₂ mixed with zeolites may open new opportunities as base supports for acid-base and oxidation reactions. These solids would endow the catalysts with specific acid sites, which may not necessarily be found in those supports with only Si-Al oxides as basic materials. Using a standard sol–gel methodology, SiO₂–TiO₂ mixtures are prepared and mixed with β, Y and ZSM-5 zeolites. By partially hydrolyzing the SiO₂ precursor at the beginning of the sol–gel procedure it is possible to maximize the number of Si–O–Ti bridges formed. FTIR and AFM analyses show that the size of sols formed depend upon the type of zeolite. Metal loading helps surface dehydroxylation of the materials, possibly indicating a good insertion of the metal into the network.