CO oxidation on Ta-Modified SnO2 solid solution catalysts

Co-precipitation method was adopted to prepare Sn–Ta mixed oxide catalysts with different Sn/Ta molar ratios and used for CO oxidation. The catalysts were investigated by N₂-Brunauer–Emmett–Teller (N₂-BET), X-ray diffraction patterns (XRD), H₂-temperature programmed reduction (H₂-TPR), Thermal Gravity Analysis – Differential Scanning Calorimetry (TGA–DSC) techniques. It is revealed that a small amount of Ta cations can be doped into SnO₂ lattice to form solid solution by co-precipitation method, which resulted in samples having higher surface areas, improved thermal stability and more deficient oxygen species on the surface of SnO₂. As a result, those Sn rich Sn–Ta solid solution catalysts with an Sn/Ta molar ratio higher than 4/2 showed significantly enhanced activity as well as good resistance to water deactivation. It is noted here that if tantala disperses onto SnO₂ surface instead of doping into its lattice, it will then have negative effect on its activity.     

The chemical changes occurring upon cycling of a SnO2 negative electrode for lithium ion cell: In situ Mössbauer investigation

Electrochemical reduction of a SnO₂ electrode for a lithium ion cell is known to result in formation of Li_4.4Sn alloy+2Li₂O. In order to determine to which extent such an electrode can be considered as reversible, we studied the electrochemical oxidation of a previously reduced SnO₂ electrode, using in situ ¹¹⁹Sn Mössbauer spectroscopy. Contrary to what could be expected, the first step does not consist in extraction of lithium from Li_4.4Sn for β-Sn to be obtained. In fact, simple lithium extraction proceeds only down to the Li_1.4Sn composition. Further oxidation (second step) involves formation of unusual species (Sn(0) and oxygen-surrounded Sn(II), both probably in interaction with Li₂O). Then (third step), red SnO-like Sn(II) species are formed, along with some Sn(IV). Especially during the second and third steps, the working electrode is far from thermodynamic equilibrium despite the low oxidation rate. This non-equilibrium behavior is probably related to the ultrafine particle size resulting from electrochemical grinding.     

Promotion of PtRu/C anode catalysts for ethanol oxidation reaction by addition of Sn modifier

PtRu/C anode electrocatalysts modified by Sn were prepared for ethanol oxidation reaction (EOR). Their phase structures, surface species, surface compositions, and EOR activities were characterized by XRD, XPS, temperature-programmed reduction (TPR), and CV, respectively. It has been found that in the PtRu/Sn_xC and PtSn/C alloy catalysts, some Sn alloyed with Pt to form Pt–Sn phase existed as the metallic state, however, the excess Sn existed as the amorphous SnO or crystalline SnO₂. Surface analyses and electrochemical measurements suggest that the surface Ru and amorphous SnO instead of the crystalline SnO₂ are important species for the promotion of EOR. As a result, compared with PtSn/C, the I₀₆ was enhanced about 200% for the PtRu/C electrocatalyst with 10 wt% of Sn modification.     

Electronic properties of Cu clusters and islands and their reaction with O2 on SnO2(110) surfaces

The deposition of Cu on SnO₂(110) surfaces, and its oxidation to Cu_xO, have been studied by low-energy electron diffraction (LEED) and angle-integrated photoemission using synchrotron radiation photoemission spectroscopy (SRPES). With the growth of copper on SnO₂(110), which was found to follow the Volmer-Weber (“islanding”) growth mode, a small amount of metal-phase Sn segregates to the surface, and even when the copper thickness reaches several tens of Å, Sn metal still is seen at the surface. But when this surface is annealed at 800 K in 5 × 10^?6 mbar O₂ for 20 min, the Sn atoms are totally converted to SnO₂. Simultaneously, the deposited Cu atoms become oxidized. The surface charges up both during LEED and SRPES data acquisition. The clean SnO₂(110) surface shows a 1 × 1 structure. With Cu deposition, the substrate LEED pattern gradually becomes weaker. With even more copper deposited, a Cu(111)-1 × 1-oriented particle structure appears, indicating coalescence of the Cu islands to 3-dimensional Cu(111) epitaxy. After subsequent heating to 500 K, the substrate signal appears again, and we see the SnO₂ 1 × 1 pattern. In conclusion, Cu atoms quite easily form clusters on the SnO₂(110) surface already after a slight heat treatment. The results show that this system is quite active towards O₂ gas exposure, and that the surface conductivity changes during O₂ exposure.     

Electrochemical and Spectroelectrochemical Analysis of 4‐(4‐(5‐Phenyl‐1,3,4‐oxadiazole‐2‐yl)phenoxy)‐Substituted Cobalt(II), Lead(II) and Metal‐Free Phthalocyanines

Electrochemical and spectroelectrochemical analyses of 4‐(4‐(5‐phenyl‐1,3,4‐oxadiazole‐2‐yl)phenoxy)‐substituted metal‐free phthalocyanine ( H₂Pc ( 1 )) and metallated phthalocyanines ( PbPc ( 2 ) and CoPc ( 3 )) were performed in solution. Voltammetric characterizations of the phthalocyanine complexes were investigated by using cyclic voltammetry and square wave voltammetry techniques. CoPc ( 3 ) gave common metal and ring based electron transfer reactions; however they split due to the aggregation. Although PbPc ( 2 ) illustrated reversible reduction processes during the voltammetric measurements, it was de‐metallized and thus turned to the metal free phthalocyanine during repetitive voltammetric cycles and in situ spectroelectrochemical measurements.     

Anodic passivation of tin in buffered phosphate electrolyte

The anodic behaviour of tin in buffered phosphate electrolyte (pH=3.1) has been studied by a variety of techniques. A number of anodic processes occur depending on potential and the conditions at the electrode/electrolyte interphase. On anodic polarisation the electrode, which is probably filmed with a phosphate layer, initially undergoes dissolution to form probably Sn(H₂PO₄·HPO₄)^? species. Impedance data indicate that this process has a corresponding Tafel slope of ～0.046 V/decade. At more positive potentials three consecutive passivating processes occur.The primary passivating process involves the blocking of the electrode by Sn₃(PO₄)₂ by a dissolution-precipitation mechanism. The formation of SnO by a slow three dimensional nucleation and growth process constitutes the second. It is formed as a result of the attainment of alkaline conditions at the electrode surface. There is also a parallel reaction path involving the formation of soluble Sn(II) species. The tertiary process consists of the oxidation of Sn to Sn(IV) species. Passivation occurs via a dissolution-precipitation mechanism when the electrode is blocked by SnO₂. The relative quantities of SnO and SnO₂ produced is a function of operating conditions.     

SnO2 negative electrode for lithium ion cell: in situ Mössbauer investigation of chemical changes upon discharge

In situ ¹¹⁹Sn Mössbauer study of an SnO₂ electrode was performed during discharge of a lithium ion cell. The first step is lithium intercalation into the SnO₂ host structure. This lithium intercalation results in reinforcement of the SnO₂ lattice instead of direct decomposition of the oxide upon reduction. This first step is followed by the reduction of tin dioxide into unusual tin species (possibly “exotic” forms of Sn(II) or Sn(0)). The last step of the discharge consists in Li-Sn alloy formation. However, non-reduced SnO₂ is present nearly up to the end of the discharge despite a very low discharge regime. It seems highly probable that this fact is related both to slow Li diffusion and disconnection of SnO₂ particles due to Li₂O formation. The working electrode appears to be rather far from equilibrium during continuous discharge, which means that ideal succession of well-defined stages cannot describe the real phenomena involved in the operating battery.     

Electrochemical Characterization of Archaeological Tin‐Opacified Lead‐Alkali Glazes and Their Corrosion Processes

The electrochemical response of weathered and unweathered archaeological tin‐opacified glazes attached to paraffin‐impregnated graphite electrodes is described. Upon comparison with the square wave voltammetric response of SnO₂, PbO and PbO₂, Sn‐ and Pb‐centered reduction processes can be characterized. Reduction of Sn(IV) involves the stepwise formation of solid Sn(II) and Sn metal, successively, at potentials of ?0.08 and ?0.55 V vs. AgCl/Ag. Reduction of network‐modifier Pb(II) in glazes occurs at ?0.5 V and is accompanied by the reduction of network‐forming Pb(IV) at potentials ranging from +0.65 to +0.20 V, confirming the presence of such centers in glazes. Voltammetric data suggest the presence of small amounts of Sn(II) resulting from the reduction of cassiterite during the firing process. A series of correlations between the peak currents can be established, indicating that the weathering process obeys a kinetic process rather than a equilibrium‐like situation.     

Nanocrystalline tin compounds/graphene nanocomposite electrodes as anode for lithium-ion battery

Nanocrystalline tin (Sn) compounds such as SnO₂, SnS₂, SnS, and graphene nanocomposites were prepared using hydrothermal method. The X-ray diffraction (XRD) pattern of the prepared nanocomposite reveals the presence of tetragonal SnO₂, hexagonal SnS₂, and orthorhombic SnS crystalline structure in the SnO₂/graphene nanosheets (GNS), SnS₂/GNS, and SnS/GNS nanocomposites, respectively. Raman spectroscopic studies of the nanocomposites confirm the existence of graphene in the nanocomposites. The transmission electron microscopy (TEM) images of the nanocomposites revealed the formation of homogeneous nanocrystalline SnO₂, SnS_2, and SnS particle. The weight ratio of graphene and Sn compound in the nanocomposite was estimated using thermogravimetric (TG) analysis. The cyclic voltammetry experiment shows the irreversible formation of Li₂O and Li₂S, and reversible lithium-ion (Li-ion) storage in Sn and GNS. The charge–discharge profile of the nanocomposite electrodes indicates the high capacity for the Li-ion storage, and the cycling study indicates the fast capacity fading due to the poor electrical conductivity of the nanocomposite electrodes. Hence, the ratio of Sn compounds (SnO₂) and GNS have been altered. Among the examined SnO₂:GNS nanocomposites ratios (35:65, 50:50, and 80:20), the nanocomposite 50:50wt% shows high Li-ion storage capacity (400 mAh/g after 25 cycles) and good cyclability. Thus, it is necessary to modify GNS and Sn compound composition in the nanocomposite to achieve good cyclability.     

NO adsorption on the stoichiometric and reduced SnO2(110) surface

The adsorption of NO molecules on the perfect and defective (110) surfaces of SnO₂ was studied with first-principles methods at the density-functional theory level. It was found that NO mainly interacts via the nitrogen atom with the bridging oxygens of the stoichiometric surface while the coordinatively unsaturated surface Sn atoms are less reactive. On the oxygen-deficient surface, NO is preferentially adsorbed at the vacancy positions, with the nitrogen atom close to the former surface oxygen site. Regardless of the adsorption site, the unpaired electron is located mainly on the NO molecule and only partly on surface Sn atoms. The results for the SnO₂ surface are compared to literature results on the isostructural TiO₂ rutile (110) surface. Dedicated to Professor Karl Jug on the occasion of his 65th birthday     

Influence of La(III) on the reactivity and sensor properties of nanocrystalline SnO<Subscript>2</Subscript>

Synthesis of Sn(IV) and La(III) based nanocomposites has been effectuated. According to the data obtained by XRD and TPR-H₂ methods, it is supposed that La in nanocompites is located in amorphous La₂Sn₂O₇ segregation. The effect of La(III) on the adsorption properties of SnO₂ surface and concentration of chemisorbed oxygen was determined. Sensor properties of obtained materials towards 10 ppm of CO in air were studied by in situ DC conductance measurements. It is shown that La introduction allows to increase sensor response of SnO₂ during CO detection in air.     

Sol鈥揼el (combustion) synthesis and characterization of different alkaline earth metal (Ca, Sr, Ba) stannates

In this study, monophasic strontium and barium stannate (SrSnO₃, Sr₂SnO₄, BaSnO₃, Ba₂SnO₄) powders were synthesized by means of environmentally friendly aqueous sol–gel technique under neutral conditions. However, it was established that the successful sol–gel synthesis of appropriate calcium stannates (CaSnO₃ and Ca₂SnO₄) can be performed only at acidic sol–gel processing conditions. Moreover, the influence of nature of alkaline earth metal source on the phase purity of different metal stannates was evaluated. The thermal behaviour of Ca–Sn–O, Sr–Sn–O and Ba–Sn–O precursor gels was investigated by TG-DSC measurements. The phase purity, crystallization peculiarities and microstructural evolution of the sol–gel derived alkaline earth metal stannate powders were studied by XRD and SEM measurements.     

A Multi-Wall Sn/SnO2@Carbon Hollow Nanofiber Anode Material for High-Rate and Long-Life Lithium-Ion Batteries

Multi-wall Sn/SnO₂@carbon hollow nanofibers evolved from SnO₂ nanofibers are designed and programable synthesized by electrospinning, polypyrrole coating, and annealing reduction. The synthesized hollow nanofibers have a special wire-in-double-wall-tube structure with larger specific surface area and abundant inner spaces, which can provide effective contacting area of electrolyte with electrode materials and more active sites for redox reaction. It shows excellent cycling stability by virtue of effectively alleviating pulverization of tin-based electrode materials caused by volume expansion. Even after 2000 cycles, the wire-in-double-wall-tube Sn/SnO₂@carbon nanofibers exhibit a high specific capacity of 986.3 mAh g⁻¹ (1 A g⁻¹) and still maintains 508.2 mAh g⁻¹ at high current density of 5 A g⁻¹. This outstanding electrochemical performance suggests the multi-wall Sn/SnO₂@ carbon hollow nanofibers are great promising for high performance energy storage systems.     

Enhancement of thin film tin oxide negative electrodes for lithium batteries

Thin films of pure SnO₂, of the Sn/Li₂O layered structure, and of Sn/Li₂O were fabricated by sputtering method, while a `lithium-reacted tin oxide thin film' was assembled by the evaporation of lithium metal onto a SnO₂ thin film. Film structure and charge/discharge characteristics were compared. The lithium-reacted tin oxide thin film, the Sn/Li₂O layered structure, and the Sn/Li₂O co-sputtered thin films did not show any irreversible side reactions of forming Li₂O and metallic Sn near 0.8 V vs Li/Li⁺. The initial charge retention of the Sn/Li₂O layered structure and Sn/Li₂O co-sputtered thin films was about 50% and a similar value was found for the lithium-reacted tin oxide thin film (more than 60%). Sn/Li₂O layered structure and Sn/Li₂O co-sputtered thin films showed better cycling behavior over 500 cycles than the pure SnO₂ and lithium-reacted tin oxide thin film in the cut-off range from 1.2 to 0 V vs Li/Li⁺.     

Fabrication of synthetic opals composed of mesoporous SnO2 spheres with an anodization-assisted double template process

Synthetic opals composed of mesoporous SnO₂ spheres were successfully fabricated from anodization of Sn opals, double templated from polystyrene opals. The mesoporous SnO₂ spheres were 440 nm in diameter containing mesopores of 20–40 nm. The resultant mesoporous SnO₂ opals possessed a high specific surface area of 196 m²/g and a grain size of 12 nm as estimated from XRD patterns. Such a hierarchical structure of SnO₂ is a promising candidate for applications in gas sensors, catalysts, and electrode materials since the regularity of the sub-micron opal structure eases transfers of relevant chemical species within the structure while the mesoporosity of the constituent SnO₂ spheres offers sufficient functioning surfaces for targeted applications.     

Temperature programmed reduction studies of spillover effect in Pd impregnated metal oxide catalysts

Temperature programmed hydrogen reduction studies have been carried out for SnO₂ and Ce-Sn mixed oxides with and without Pd metal impregnation, to demonstrate the existence of spillover of hydrogen from Pd metal centers to support oxides. TPR pattern of SnO₂ showed a main peak at 973 K indicating the bulk reduction of this sample. In Pd metal impregnated sample, the bulk reduction peak shifts to lower temperature (923 K) due to the spillover of activated hydrogen from Pd metal to SnO₂ at relatively lower temperatures and its subsequent reaction with SnO₂. For Pd impregnated Ce-Sn mixed oxide samples also, a similar effect or an enhanced reduction was observed indicating the spillover effect of hydrogen. These results have been further confirmed from ¹¹⁹Sn Mössbauer spectroscopic measurements carried out for some representative samples of SnO₂ and Pd/SnO₂ heated in hydrogen flow up to a temperature of 473 K. The value of Sn²⁺/(Sn₄₊+Sn₂₊) ratio was found to be significantly higher for Pd impregnated sample. Both these observations provide direct evidence for the existence of spillover effect of hydrogen taking place in the metal impregnated samples.     

Novel peripherally tetra substituted metal-free,cobalt(II), copper(II) and manganese(III) phthalocyanines bearing polyethoxy chain attached by 2,6-diphenylphenol groups: synthesis,characterization and their electrochemical studies

Metal free (6), cobalt(II) (7), copper(II) (8) and manganese(III) (9) phthalocyanines, which are tetra substituted at the peripheral positions with 2-[2-(1,1′:3′,1′′-terphenyl-2′-yloxy)ethoxy]ethoxy groups, were synthesized and characterized by IR, ¹H-NMR,¹³C-NMR, UV–Vis and mass spectroscopy. Electrochemistry of the phthalocyanines were studied with voltammetric measurements by using cyclic voltammetry and square wave voltammetry techniques in DCM/TBAP electrolyte on a Pt working electrode. Electrochemical measurements exhibit that incorporation of redox active metal ions, Co^II and Mn^III, into the phthalocyanine core extends the redox capabilities of the Pc ring including the metal-based reduction couples of the metal. While Mn^IIIClPc showed only metal based reduction reactions, Co^IIPc showed metal based and ligand based reduction reactions as expected. Cyclic and square wave voltammetric studies showed that phthalocyanines have reversible/quasireversible/irreversible redox processes, which are the main requirement for the technological usage of these compounds.     

Characterization of tin coated Al alloy by 119Sn conversion electron Mössbauer spectrometry (CEMS)

Sn-plating of aluminum alloy before and after a post-molybdate treatment is characterized by ¹¹⁹Sn conversion electron Mössbauer spectrometry (CEMS). CEMS results gave the direct evidence that the oxidation resistance of Sn-coated aluminum alloy is improved by the post-molybdate treatment. Depth selective CEMS showed that the coating structures consist of SnO₂ on the top coating and the mixed Sn(0) and Sn(II) species in the intermediate layers. The Sn(II) oxide exists abundantly near the interface between the aluminum alloy and the Sn coating rather than beneath SnO₂ layer.     

Transition‐Metal‐Catalyzed Oxidation of Metallic Sn in NiO/SnO2 Nanocomposite

It is well accepted that metallic tin as a discharge (reduction) product of SnO_x cannot be electrochemically oxidized below 3.00 V versus Li⁺/Li⁰ due to the high stability of Li₂O, though a similar oxidation can usually occur for a transition metal formed from the corresponding oxide. In this work, nanosized Ni₂SnO₄ and NiO/SnO₂ nanocomposite were synthesized by coprecipitation reactions and subsequent heat treatment. Owing to the catalytic effect of nanosized metallic nickel, metallic tin can be electrochemically oxidized to SnO₂ below 3.00 V. As a result, the reversible lithium‐storage capacities of the nanocomposite reach 970 mAh g^?1 or above, much higher than the theoretical capacity (ca. 750 mAh g^?1) of SnO₂, NiO, or their composites. These findings extend the well‐known electrochemical conversion reaction to non‐transition‐metal compounds and may have important applications, for example, in constructing high‐capacity electrode materials and efficient catalysts.     

Pt-doped semiconductive oxides loaded on mesoporous SBA-15 for gas sensing

SBA-15-based solids combining semiconductive oxides (Sn and In) and noble metal (Pt) were prepared by an incipient wet impregnation method in order to obtain materials for gas sensing. The materials were characterized by XRD, BET adsorption, SEM, and TEM. The BET analysis allowed obtaining details about the specific surface areas, pore size, and modifications due to the indium and/or tin oxides followed by the Pt deposition. XRD data revealed that In₂O₃ did not enter the mesopores of SBA-15, preventing also the entrance of the Pt nanoparticles in the mesopores. On the other hand, SnO₂ nanoparticles further doped with Pt could enter the mesoporous network, affording a SBA-15 material loaded with SnO₂ and very small Pt nanoparticles with high dispersion. Tablets obtained by pressing the modified SBA-15 were tested as sensitive materials for propene and hydrogen detection.