Titania nanotube supported tin anodes for lithium intercalation

A new type of nanostructured titania nanotube supported tin anode was prepared for lithium ion batteries. The as-prepared titania nanotubes are in the anatase phase with diameters of about 12 nm. Tin nanoparticles are dramatically decorated on the titania nanotubes and have a particle size of about 10 nm. This new structure promises good retention of reversible capacity on cycling for lithium intercalation. By charge/discharge measurements, the reversible capacity of the titania nanotubes supported tin anode for lithiation and de-lithiation was found to be 312 mA h/g (cycled between 0.05 and 2.0 V) and 203 mA h/g (cycled between 0.05 and 1.3 V) after 50 cycles with around 100% columbic efficiency.     

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC₅H₁₁)₄]₂ [M = Y and Pr–Lu except Pm; H₂Pc(α-OC₅H₁₁)₄ = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC₅H₁₁)₄]₂ are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)₂ and M[Pc(OC₈H₁₇)₈]₂, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC₅H₁₁)₄], revealing the decreased molecular symmetry of these double-decker compounds, namely S₈. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm⁻¹, the IR spectra of M[Pc(α-OC₅H₁₁)₄]₂ are quite similar to those of corresponding M(Pc)[Pc(α-OC₅H₁₁)₄] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm⁻¹ are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH₃ groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′⁻ IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)₂ > M(Pc)[Pc(α-OC₅H₁₁)₄] > M[Pc(α-OC₅H₁₁)₄]₂, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.     

Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.     

Study of photoanode kinetics at metal-free phthalocyanine in an organic p/n bilayer with respect to the pH conditions employed

Using an organic p/n bilayer comprised of 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, an n-type semiconductor) and 29H,31H-phthalocyanine (H₂Pc, a p-type semiconductor) as a photoanode in the presence of Fe^II(CN)₆^4? (an electron donor), the oxidation kinetics on the H₂Pc surface was investigated with respect to the pHs employed (i.e. pH = 4, 7, and 10). The kinetic analysis of the rate-limiting charge transfer between H₂Pc and Fe^II(CN)₆^4? was conducted by assuming the Langmuir adsorption equilibrium at the H₂Pc/water interface. In addition to a demonstration of the PTCBI/H₂Pc photoanode under the weakly acidic–alkaline conditions, the present work evidently shows that the photoanodic reaction is kinetically independent of the pH conditions employed.     

Visible light photocatalysis by a Titania–Rhodium(III) complex

Titania hybrid photocatalysts containing 0.5, 1.0, 2.0, and 5.0 wt% of rhodium(III) were prepared by chemisorption of RhCl₃ × 3H₂O onto anatase hydrate powder (TH). Analytical data suggest that a titania–trichlororhodate complex is produced containing a [TiO₂]–O–Rh bond.Similar results are found in the case of modification by RhBr₃ × 3H₂O. Diffuse reflectance spectra exhibit an absorption shoulder throughout the visible region down to 700 nm. Photoelectrochemical measurements indicate that the quasi-Fermi level of electrons is gradually shifted to more anodic potentials with increasing rhodium loading reaching a value of ?0.34 V at pH 7 (vs. NHE) in the case of 5.0%RhCl₃/TH. This is more anodic by 210 mV as compared to unmodified TH. Upon visible light irradiation this photocatalyst induces a fast mineralization of 4-chlorophenol whereas cyanuric acid, which is known to be mineralized in the presence of the analogous Pt(IV) modified titania, is not degraded.     

Thermal stability of TiO2-anatase: Impact of nanoparticles morphology on kinetic phase transformation

TiO₂ is a material of great interest for many technological applications among which, as catalyst support. As this specific application requires a good thermal stability of the material, the phase transition between the two most commonly used titania polymorphs, anatase and rutile, has been extensively studied over the past decade. However not much importance has been given to the initial and final particles morphologies. In this study, anatase nanoparticles with an elongated shape were synthesized and their kinetic phase transformation was studied. The thermal treatments were conducted at temperatures ranging from 500 to 700 °C. The morphology evolution and the phase transition were characterized by X-ray diffraction and transmission electron microscopy. The phase transformation kinetics is best described by the interface nucleation models. The values of the measured kinetic parameters are significantly lower than those proposed in the literature for isotropic particles, with an activation energy of E_a = 345 kJ mol^?1. The influence of morphology and, as a consequence, the influence of exposed faces on anatase particles, are presented and discussed.     

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes. Part 15: The IR characteristics of phthalocyanine in homoleptic tetrakis(phthalocyaninato) rare earth(III)-cadmium(II) quadruple-deckers

The infra-red (IR) spectroscopic data for a series of twelve sandwich-type homoleptic tetrakis[2,3,9,10,16,17,23,24-octa(octyloxy)phthalocyaninato] rare earth(III)-cadmium(II) quadruple-decker complexes [Pc(OC₈H₁₇)₈]M[Pc(OC₈H₁₇)₈]Cd[Pc(OC₈H₁₇)₈]M[Pc(OC₈H₁₇)₈] (M = Y, Pr–Yb except Pm) have been collected with resolution of 2 cm⁻¹ and their interpretation in terms tried by analogy with the IR characteristics of bis(phthalocyaninato) cerium double-decker [Pc(OC₈H₁₇)₈]Ce[Pc(OC₈H₁₇)₈] in which the macrocyclic ligands exist as the phthalocyanine dianion. Similar to the bis/tris(phthalocyaninato) rare earth sandwich counterparts, all the absorptions contributed primarily by or at least containing contribution from the vibrations of pyrrole or isoindole stretching, breathing or deformation or aza stretching in the IR spectra of these quadruple-decker compounds show dependent nature on the rare earth ionic size. The shift toward higher energy direction in the frequencies of these vibrations along with the decrease of the rare earth radii reveals the effective and increasing π–π interactions in these quadruple-decker sandwich compounds in the same order. Nevertheless, the decreased sensitivity of the frequencies of the above mentioned vibration modes in particular the weak absorption band due to the isoindole stretching at 1414–1416 cm⁻¹ for the quadruple-decker on rare earth metal size in comparison with corresponding band for bis(phthalocyaninato) rare earth counterparts indicates the relatively weaker π–π interaction in these quadruple-deckers than in the double-deckers.     

Glucose biosensor based on new carbon nanotube-gold-titania nano-composites modified glassy carbon electrode

In this paper, a novel biosensor was prepared by immobilizing glucose oxidase （GOx） on carbon nanotube-gold-titania nanocomposites （CNT/Au/TiO2） modified glassy carbon electrode （GCE）. SEM was initially used to investigate the surface morphology of CNT/Au/TiO2 nanocomposites modified GCE, indicating the formation of the nano-porous structure which could readily facilitate the attachment of GOx on the electrode surface. Cyclic voltammogram （CV） and electrochemical impedance spectrum （EIS） were further utilized to explore relevant electrochemical activity on CNT]Au/TiO2 nanocomposites modified GCE. The observations demonstrated that the immobilized GOx could efficiently execute its bioelectrocatalytic activity for the oxidation of glucose. The biosensor exhibited a wider linearity range from 0.1 mmol L-1 to 8 mmol L^-1 glucose with a detection limit of 0.077 mmol L^- 1.     

Characterization and source term assessments of radioactive particles from Marshall Islands using non-destructive analytical techniques

Six plutonium-containing particles stemming from Runit Island soil (Marshall Islands) were characterized by non-destructive analytical and microanalytical methods. Composition and elemental distribution in the particles were studied with synchrotron radiation based micro X-ray fluorescence spectrometry. Scanning electron microscope equipped with energy dispersive X-ray detector and with wavelength dispersive system as well as a secondary ion mass spectrometer were used to examine particle surfaces. Based on the elemental composition the particles were divided into two groups: particles with pure Pu matrix, and particles where the plutonium is included in Si/O-rich matrix being more heterogenously distributed. All of the particles were identified as nuclear fuel fragments of exploded weapon components. As containing plutonium with low ²⁴⁰Pu/²³⁹Pu atomic ratio, less than 0.065, which corresponds to weapons-grade plutonium or a detonation with low fission yield, the particles were identified to originate from the safety test and low-yield tests conducted in the history of Runit Island. The Si/O-rich particles contained traces of ¹³⁷Cs (^239 + 240Pu/¹³⁷Cs activity ratio higher than 2500), which indicated that a minor fission process occurred during the explosion. The average ²⁴¹Am/²³⁹Pu atomic ratio in the six particles was 3.7 × 10^− 3 ± 0.2 × 10^− 3 (February 2006), which indicated that plutonium in the different particles had similar age.     

Dye-sensitized solar cells using anodic TiO2 mesosponge: Improved efficiency by TiCl4 treatment

In the present work, we produce 15 μm thick titania mesosponge layers (TMSL) by a Ti anodization/etching process and use the layers in dye-sensitized solar cells (DSCs). We show that the solar cell efficiency can considerably be improved by a TiCl₄ hydrolysis treatment (increase of approx. 40% to an overall value of 4.9% under AM 1.5 illumination). This beneficial effect is due to the decoration of the ～10 nm wide channels present in TMSL with TiO₂ nanoparticles of approx. 3 nm diameter, which allow for a significantly higher specific dye loading of the TMS structure.     

Demonstration of a novel,flexible, photocatalytic oxygen-scavenging polymer film

The preparation of a novel, flexible, photocatalytic, oxygen-scavenging polymer film is described. The film incorporates nanocrystalline titania particles in an ethyl cellulose polymer film, with or without an added sacrificial electron donor of triethanolamine. When coated on the inside of a glass vessel its UV-driven light-scavenging action is demonstrated by platinum octaethyl porphyrin coated glass beads sealed inside, since their luminescence increases with increasing UV-irradiation time. When used as a flexible film, work with an oxygen electrode shows that the film is able to scavenge oxygen at an average rate of 0.017 cm³ O₂ h⁻¹ cm⁻² over a 24 h period, which compares favourably to other, well-established oxygen-scavenger systems. The potential of using such as system for oxygen scavenging in packaging is discussed briefly.     

Surface plasmon resonance biosensor based on Au nanoparticle in titania sol–gel membrane

A novel surface plasmon resonance (SPR) biosensor for the determination of human IgG was introduced. The biosensor was prepared with three layers of titania sol–gel membrane by vapor deposition. The colloid Au nanoparticle (AuNP) was immobilized in the second layer of titania membrane and the AuNP coupled with rabbit anti-human IgG was encapsulated in the third layer. The AuNP in the second layer of titania membrane was proved to be effective in the sensitivity enhancement of SPR biosensor. The lowest concentration that could be detected obtained by the biosensor with AuNP is about eight times lower than that obtained without AuNP. In addition, the titania sol–gel is a porous homogeneous material that permits analytes to access the encapsulated biomolecule and can provide a controlled environment for the study of biomolecular recognition. The titania sol–gel was also confirmed to be benefit for biomolecule to keep bioactivity, which could offer a good waterish microenvironment. As a result, the modified biosensor exhibits a satisfactory response for human IgG in the concentration range of 0.30–40.00 μg mL^?1 and shows favorable bioactivity for a long time.     

Chemical vapor generation of silver for atomic absorption spectrometry with the multiatomizer: Radiotracer efficiency study and characterization of silver species

Volatile Ag species were generated in flow injection arrangement from nitric acid environment in the presence of surfactants (Triton X-100 and Antifoam B) and permanent Pd deposits as the reaction modifiers. Atomic absorption spectrometry (AAS) with multiple microflame quartz tube atomizer heated to 900 °C was used for atomization; evidence was found for thermal mechanism of atomization. Relative and absolute limits of detection (3σ, 250 μl sample loop) measured under optimized conditions were: 1.4 μg l^? 1 and 0.35 ng, respectively.The efficiency of chemical vapor generation (CVG) as well as spatial distribution of residual analyte in the apparatus was studied by ¹¹¹Ag radioactive indicator (half-life 7.45 days) of high specific activity. It was found out that 23% of analyte was released into the gaseous phase. However, only 8% was found on filters placed at the entrance to the atomizer due to transport losses. About 40% of analyte remained in waste liquid, whereas the rest was found deposited over the CVG system.Presented study follows the hypothesis that the “volatile” Ag species are actually metallic nanoparticles formed upon reduction in liquid phase and then released with good efficiency to the gaseous phase. Number/charge size distributions of dry aerosol were determined by Scanning Mobility Particle Sizer. Ag was detected in 40–45 nm particles holding 10 times more charge if compared to Boltzmann equilibrium. At the same time, Ag was also present on 150 nm particles, the main size mode of the CVG generator. The increase of Ag in standards was reflected by proportional increase in particle number/charge for 40–45 nm size particles only.Transmission electron microscopy revealed particles of 8 ± 2 nm sampled from the gaseous phase, which were associated in isolated clusters of few to few tens of nanometres. Ag presence in those particles was confirmed by Energy Dispersive X-ray Spectroscopy (EDS) analysis.     

Low temperature preparation of anatase TiO2-coated activated carbon

Anatase titania sols were synthesized at low temperature (i.e. 75 °C) by hydrolysis of titaniumn-butoxide in abundant acidic aqueous solution. The prepared TiO₂ nanoparticles were loaded on activated carbon in a rotatory evaporator under vacuum, and then the composite photocatalyst was employed for the removal of phenol from water. The apparent rate constant and quantum yield of the composite photocatalyst enhanced 5 and 2.5 times, respectively, compared to single phase titania. The activated carbon with strong adsorbent activity provided sites for the adsorption of phenol, and the adsorbed phenol migrated continuously onto the surface of TiO₂ particles which were located mainly at the exterior surface of the activated carbon. Some phenol remained adsorbed on the catalyst when no traces of phenol were detected in the water. This adsorbed phenol could be degraded by illuminated titania while maintaining UV-irradiation. The photocatalyst was used for six cycles with degraded rate of phenol still higher than 80%.     

Preparation of spherical silica particles by Stöber process with high concentration of tetra-ethyl-orthosilicate

In this paper, Stöber process with high concentration of tetra-ethyl-orthosilicate (TEOS) up to 1.24 M is used to prepare monodisperse and uniform-size silica particles. The reactions are carried out at [TEOS] = 0.22–1.24 M, low concentrations of ammonia ([NH₃] = 0.81[TEOS]), and [H₂O] = 6.25[TEOS] in isopropanol. The solids content in the resulting suspension achieves a maximum value of 7.45% at 1.24 M TEOS. Various-sized particles in the range of 30–1000 nm are synthesized. The influences of TEOS, NH₃, and H₂O on the size and size distribution of the particles are discussed. A modified monomer addition model combined with aggregation model is proposed to analyze the formation mechanism of silica particles.     

Graphene supported Sn–Sb@carbon core-shell particles as a superior anode for lithium ion batteries

This paper reports the preparation and Li-storage properties of graphene nanosheets(GNS), GNS supported Sn–Sb@carbon (50–150 nm) and Sn–Sb nanoparticles (5–10 nm). The best cycling performance and excellent high rate capabilities were observed for GNS-supported Sn–Sb@carbon core-shell particles, which exhibited initial capacities of 978, 850 and 668 mAh/g respectively at 0.1C, 2C and 5C (1C = 800 mA/g) with good cyclability. Besides the GNS support, the carbon skin around Sn–Sb particles is believed to be a key factor to improve electrochemical properties of Sn–Sb.     

Study of near infra red femtosecond laser induced particles using transmission electron microscopy and low pressure impaction: Implications for laser ablation–inductively coupled plasma-mass spectrometry analysis of natural monazite

The characteristics of infra red femtosecond laser-induced aerosols are studied for monazite (LREE, Th(PO₄)) ablation and correlations are established with inductively coupled plasma-mass spectrometry (ICP-MS) signals. Critical parameters are tested within wide ranges of values in order to cover the usual laser ablation -ICP-MS analysis conditions: pulse energy (0.15 < E₀ < 1 mJ/pulse), pulse width (60 < τ < 3000 fs), ablation time (t ≤ 10 min) and transport length (l ≤ 6.3 m). Transmission electron microscopy reveals that aerosols are made of agglomerates of ~ 10 nm particles and 20–300 nm phosphorus depleted condensed spherical particles. These structures are not affected by any laser ablation parameter. Particle counting is performed using electronic low pressure impaction. Small changes on particle size distribution are noticed. They may be induced either by a peak of ablation rate in the first 15 s at high fluence (larger particles) or the loss of small particles during transport. We found a positive correlation between I (ICP-MS mean signal intensity in cps) and N (particle density in cm^? 3) when varying E₀ and t, suggesting that N is controlled by the irradiance (P₀ in W·cm^? 2). Elemental ratio measurements show a steady state signal after the initial high ablation rate (mass load effect in the plasma torch) and before a late chemical fractionation, induced by poor extraction of bigger, early condensed spherical particles from the deepening crater. Such chemical fractionation effects remain within uncertainties, however. These effects can be limited by monitoring E₀ to shorten the initial transient state and delay the attainment of an unfavorable crater aspect ratio. Most adopted settings are for the first time deduced from aerosol characteristics, for infra red femtosecond laser ablation. A short transport (l < 4.0 m) limits the agglomeration of particles by collision process along the tube. Short τ is preferred because of higher P₀, yet no benefit is found on ICP-MS signal intensity under 200 fs. Under such pulse widths the increased particle production induces more agglomeration during transport, thereby resulting in higher mass load effects that reduce the ionization efficiency of the plasma torch. Thus, pulse energy must be set to get an optimal balance between the need for a high signal/background ratio and limitation of mass load effects in the plasma torch.     

Spectral broadening in quantum dots-sensitized photoelectrochemical solar cells based on CdSe and Mg-doped CdSe nanocrystals

In order to absorb a broad spectrum in visible region, a co-sensitized TiO₂ electrode was prepared by CdSe and Mg-doped CdSe quantum dots (Q dots). The power conversion efficiency of the co-sensitized Q dots photoelectrochemical solar cells (PECs) showed 1.03% under air mass 1.5 condition (I = 100 mW/cm²), which is higher than that of individual Q dots-sensitized PECs. The incident-photon-to-current conversion efficiency of the co-sensitized PECs showed absorption peaks at 541 and 578 nm corresponding to the two Q dots and displayed a broad spectral response over the entire visible spectrum in the 500–600 nm wavelength domains.     

Photocurrent generated on a carotenoid-sensitized TiO2 nanocrystalline mesoporous electrode

Photocurrent was observed upon monochromatic illumination of an ITO electrode coated with a TiO₂ nanocrystalline mesoporous membrane with carotenoid 8′-apo-β-caroten-8′-oic acid (ACOA) deposited as a sensitizer (illuminated area 0.25 cm²) and immersed in an aqueous 10 mM hydroquinone (H₂Q), 0.1 M NaH₂PO₄ solution (pH = 7.4) purged with argon, using a platinum flag counter electrode (area 3.3 cm²) and a SCE reference electrode. The carotenoid-sensitized short-circuit photocurrent reached 4.6 μA/cm² upon a 40 μW/cm² incident light beam at 426 nm, with an IPCE (%, incident monochromatic photon-to-photocurrent conversion efficiency) as high as 34%. The short-circuit photocurrent was stable during 1 h of continuous illumination with only a 10% decrease. An open-circuit voltage of 0.15 V was obtained (upon 426 nm, 40 μW/cm² illumination) which remained at a constant value for hours. The observed open-circuit voltage is close to the theoretical value (0.22 V) expected in such a system. The action spectrum resembled the absorption spectrum of ACOA bound on the TiO₂ membrane with a maximum near 426 nm. No decay of the ACOA on the TiO₂ surface was observed after 12 h, presumably because of rapid regeneration of ACOA from ACOA⁺ at the surface by electron transfer from H₂Q.     

Source term identification of environmental radioactive Pu/U particles by their characterization with non-destructive spectrochemical analytical techniques

Six radioactive particles stemming from Thule area (NW-Greenland) were investigated by gamma-ray and L X-ray spectrometry based on radioactive disintegration, scanning electron microscopy coupled with energy-dispersive and wavelength-dispersive X-ray spectrometer, synchrotron radiation based techniques as microscopic X-ray fluorescence, microscopic X-ray absorption near-edge structure (μ-XANES) as well as combined X-ray absorption and fluorescence microtomography. Additionally, one particle from Mururoa atoll was examined by microtomography. From the results obtained, it was found out that the U and Pu were mixed in the particles. The U/Pu intensity ratios in the Thule particles varied between 0.05 and 0.36. The results from the microtomography showed that U/Pu ratio was not homogeneously distributed. The ²⁴¹Am/^{238 + 239 + 240}Pu activity ratios varied between 0.13 and 0.17, indicating that the particles originate from different source terms. The oxidation states of U and Pu as determined by μ-XANES showed that U(IV) is the preponderant species and for Pu, two types of particles could be evidenced. One set had about 90% Pu(IV) while in the other the ratio Pu(IV)/Pu(VI) was about one third.