TPD and ITPD study of materials used as chemoresistive gas sensors

Temperature-programmed desorption (TPD) and a differential form of it, called intermittent temperature-programmed desorption (ITPD), turned out to be powerful characterising techniques for chemoresistive materials applied to gas sensing. We investigated samples of SnO₂, TiO₂ and solid solutions of them (Ti_xSn_1 ? xO₂). TPD and ITPD experiments were carried out in vacuum, with samples previously treated in pure O₂ (100 Torr, 500 °C, 30 min). Amounts of desorbed O₂ corresponded for all Ti-containing samples to less than 10% of a compact monolayer of ions O^2?. Corresponding values of the apparent activation energy of desorption (E_app) were calculated directly from the Arrhenius plots for each partial TPD and ranged from about 100 to 330 kJ mol^? 1 (1.16 to 3.82 eV).     

Conductivity of SnP2O7 and In-doped SnP2O7 prepared by an aqueous solution method

SnP₂O₇ and In-doped SnP₂O₇ have been prepared by an aqueous solution method using (NH₄)₂HPO₄ as phosphorous source. It was found that the solid solution limit in Sn_1 ? xIn_x(P₂O₇)_1 ? δ was at least x = 0.12. All pyrophosphates in the Sn_1 ? xIn_x(P₂O₇)_1 ? δ (x ≤ 0.12) series exhibit 3 × 3 × 3 superlattice structures. The conductivities of Sn_0.92In_0.08(P₂O₇)_1 ? δ in air are 6.5 × 10^? 6 and 8.0 × 10^? 9 S/cm at 900 and 400 °C, respectively, when prepared by an aqueous solution method and annealed at 1000 °C. The conductivity of undoped SnP₂O₇ is slightly lower. However, it was also found that the low-temperature conductivities of pyrophosphates annealed only at 650 °C are several orders of magnitude higher than those annealed at 1000 °C, which could be related to a trace amount of an amorphous secondary phase. The peak conductivity was in this case observed at around 250 °C, which is the same temperature as previously observed in In-doped SnP₂O₇ although the conductivity is still three orders of magnitude lower in the present study. These differences can be related to large differences in particle size and morphology, and all in all, the conductivities of SnP₂O₇-based materials are very sensitive to the synthetic history.     

Theoretical study of the (110) surface of Sn1 - xTixO2 solid solutions with different distribution and content of Ti

The composition and thermodynamic stability of the (110) surface of Sn_1 - xTi_xO₂ rutile solid solutions was investigated as a function of Ti-distribution and content up to the formation of a full TiO₂ surface monolayer. The bulk and (110) surface properties of Sn_1 - xTi_xO₂ were compared to that of the pure SnO₂ and TiO₂ crystal. A large supercell of 720 atoms and a localized basis set based on the Gaussian and plane wave scheme allowed the investigation of very low Ti-content and symmetry. For the bulk, optimization of the crystal structure confirmed that up to a Ti-content of 3.3 at.%, the lattice parameters (a, c) of SnO₂ do not change. Increasing further the Ti-content decreased both lattice parameters down to those of TiO₂. The surface energy of these solid solutions did not change for Ti-substitution in the bulk of up to 20 at.%. In contrast, substitution in the surface layer rapidly decreased the surface energy from 0.99 to 0.74 J/m² with increasing Ti-content from 0 to 20 at.%. As a result, systems with Ti atoms distributed in the surface (surface enrichment) had always lower energies and thus were thermodynamically more favorable than those with Ti homogeneously distributed in the bulk. This was attributed to the lower energy necessary to break the TiO bonds than SnO bonds in the surface layer. In fact, distributing the Ti atoms homogeneously or segregated in the (110) surface led to the same surface energy indicating that restructuring of the surface bond lengths has minimal impact on thermodynamic stability of these rutile systems. As a result, a first theoretical prediction of the composition of Sn_1 - xTi_xO₂ solid solutions is proposed.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Structure,optical, and magnetic properties of rutile Sn1−xMnxO2 thin films

Sn_1?xMn_xO₂ (x ≤ 0.11) thin films were fabricated by sol–gel and spin-coated method on Si (1 1 1) substrate. X-ray diffraction revealed that single-phase rutile polycrystalline structure was obtained for x up to about 0.078. Evolution of the lattice parameters and X-ray photoelectron spectroscopy studies confirmed the incorporation of Mn³⁺ cations into rutile SnO₂ lattice. Optical transmission studies show that the band gap energy (E_g) broadens with the increasing of Mn content. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism (RTFM), which is identified as an intrinsic characteristic. Interestingly, the magnetic moment per Mn atom decreases with the increasing Mn content. The origin of RTFM can be interpreted in terms of the bound magnetic polaron model.     

Modification of B-site doping of perovskite LaxSr1 − xFe1 − y−zCoyCrzO3 − δ oxide by Mg2+ ion

Co-doping B-site of perovskite oxide La_xSr_1 ? xCo_yFe_1 ? yO_3 ? δ (LSCFO) with Cr⁶⁺ and Mg²⁺ ions has been attempted in this research for revamping chemical stability and oxygen ionic conductivity of this mixed conducting oxide. It is known that partial substitution for B-site cations of LSCFO by Cr gives rise to a significant improvement on chemical and thermal stability of the perovskite oxide. On the basis of this doped structure, introduction of an immaterial dose of Mg²⁺ ion into its B-site results in a microstructure consisting of smaller grains with higher density than its precursor. Furthermore, the resulting perovskite oxide La_0.19Sr_0.8Fe_0.69Co_0.1Cr_0.2 Mg_0.01O_3 ? δ (LSFCCMO) displays higher O^2? conductivity than the solely Cr-doped LSCFO besides the improved chemical stability against reduction in 5% CH₄/He stream at 850 °C. A detailed examination of the oxidation states of B-site transition metal ions by XPS has also been conducted as a part of structural characterizations of LSFCCMO. The assessment of relative O^2? conductivity shows that the grain boundary area plays a more important role than the bulk phase in facilitating ion transport, but with comparable boundary areas the higher densification level is favorable.     

Field-assisted sustainable O− ion emission from fluorine-substituted 12CaO·7Al2O3 with improved thermal stability

We examined the electric field-assisted thermionic emission of atomic oxygen radical anion (O^?) in a vacuum from fluorine-substituted derivatives of 12CaO·7Al₂O₃ (C12A7) with a composition of (12 ? x)CaO·7Al₂O₃·xCaF₂ (0 ≤ x ≤ 0.8). Unsubstituted C12A7 easily decomposed into 5CaO?3Al₂O₃ (C5A3) and 3CaO?Al₂O₃ (C3A) above 830 °C during the emission experiment in a vacuum. The decomposition temperature range became narrower as the amount of F^? ion substitution increased, e.g. the sample with x = 0.4 kept a single phase after the emission experiment at 900 °C. The emitted anionic species from the x = 0.4 sample were dominated by O^? ions (～ 92%) together with a small amount of O₂^? ions (～ 4%) and F^? ions (～ 4%). The absence of an O₂ gas supply to the opposite side of the emission surface led to a nearly steady co-emission of O^? ions and electrons with a ratio of < 1/1. The O₂ gas supply markedly enhanced the O^? ion emission, and suppressed the electron emission. A sustainable and high-purity O^? ion emission with a current density of 11 nA cm^? 2 was achieved at 830 °C with the supply of 40 Pa O₂ gas. The similarity in these emission features to the unsubstituted C12A7, together with the improved thermal stability demonstrates that the F^? ion-substituted C12A7 is a promising material for higher intensity O^? ion emission at higher temperatures.     

Structural,electrical and magnetic properties of (Fe,Co) co-doped SnO2 diluted magnetic semiconductor nanostructures

Nanostructures (NSs) of basic composition Sn_1−xFe_x/2Co_x/2O₂ with x=0.00, 0.04, 0.06, 0.08 and 0.1 were synthesized by citrate-gel route and characterized to understand their structural, electrical and magnetic properties. X-ray diffraction and Raman spectroscopy were used to confirm the formation of single phase rutile type tetragonal structure. The crystallite sizes calculated by using Williamson Hall were found to decrease with increasing doping level. In addition to the fundamental Raman peaks of rutile SnO₂, the other three weak Raman peaks at about 505, 537 and 688 cm⁻¹ were also observed. Field emission scanning electron microscopy studies showed the emergence of structural transformation. Electric properties such as dc electrical resistivity as a function of temperature and ac conductivity as a function of frequency were also studied. The variation of dielectric properties with frequency reveals that the dispersion is due to Maxwell–Wagner type of interfacial polarization in general. Hysteresis loops were clearly observed in M–H curves of Fe and Co co-doped SnO₂ NSs. However, pure SnO₂ nanoparticles (NPs) showed paramagnetic behaviour which vanished at higher values of magnetic field. The grain and grain boundary contribution in the conduction process is estimated through complex impedance plot fitted with non-linear least square (NLLS) approach which shows that the role of grain boundaries increases rapidly as compared to the grain volume with the increase of Fe and Co ions in to system.     

Electrical conductivity and thermal expansion of the oxy-cuspidine Gd4Al2O9 substituted with Ca and Sr

The series of Gd_4 ? xM_xAl₂O_9 ? x/2 (M = Ca, Sr) with x = 0, 0.01, 0.05, 0.10 and 0.25 was prepared by the citrate complexation method. Both Gd_4 ? xCa_xAl₂O_9 ? x/2 and Gd_4 ? xSr_xAl₂O_9 ? x/2 show the monoclinic cuspidine structure with space group of P2₁/c up to 0.05–0.1 and 0.01–0.05 mol for Ca and Sr, respectively. Beyond the substitution limit of Gd₄Al₂O₉, GdAlO₃ and SrGd₂Al₂O₇ appear as additional phases. The highest electrical conductivity obtained at 900 °C yielded σ = 1.49 × 10^? 4 S/cm for Gd_3.95Ca_0.05Al₂O_8.98. In comparison, the conductivity of pure Gd₄Al₂O₉ was σ = 1.73 × 10^? 5 S/cm. The conductivities determined are in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd₄Al₂O₉ at 1000 °C was 7.4 × 10^? 6 K^? 1. The phase transition between 1100 and 1200 °C reported earlier changes with increasing substitution of Ca and Sr.     

The studies on structural and thermal properties of delithiated LixNi1/3Co1/3Mn1/3O2 (0 < x ≤ 1) as a cathode material in lithium ion batteries

The structural and thermal properties of the delithiated Li_xNi_1/3Co_1/3Mn_1/3O₂ (0 < x ≤ 1) material have been investigated by using diffraction and thermoanalytical techniques such as XRD and TG-DSC methods. XRD result shows that the delithiated materials maintain the O3-type structure with defined stoichiometric number at the range of 0.24 < x ≤ 1, exhibiting good crystal structural stability. The cobalt and nickel ions in the delithiated materials change their valence state (i.e. Co³⁺ to Co⁴⁺ and Ni³⁺ to Ni⁴⁺) when x < 0.49; the irreversible changes of the transformation may affect the first cycle of charge–discharge efficiency of the materials. A comparison of the results of TG-DSC with TPD-MS shows that the irreversible change of oxygen species during the delithiation process of Li_xNi_1/3Co_1/3Mn_1/3O₂ have great influence on the structural and thermal stability and reversibility of the materials.     

Lithium insertion into nanometer-sized rutile-type TixSn1 − xO2 solid solutions

The electrochemical properties of rutile-type Ti_xSn_1?xO₂ solid solutions (x = 0–1.0) as an anode for a lithium–ion battery were investigated using nanosized crystals prepared by an aqueous solution process. The reduction of the crystal size to nanoscale allowed a smooth lithium insertion into the rutile framework at room temperature. The lithium-insertion behavior of TiO₂, SnO₂, and the solid solutions was evaluated without any structural change of the rutile-type crystal structure in the potential range of 1.2–3.5 V (versus Li/Li⁺). The interstitial spaces for lithium ions were found to be derived from the crystal structure of the rutile framework and independent of the metal species.     

Significant enhancement of electrical transport properties of thermoelectric Ca3Co4O9+δ through Yb doping

We report the significant enhancement of the power factor of Ca₃Co₄O_9+δ through Yb doping. The pellets were prepared by pressing under 0.5 GPa and 2 GPa. The highest power factor of 553 μW m^?1 K^?2 due to the significant increase of electrical conductivity was obtained for Ca_2.9Yb_0.1Co₄O_9+δ pressed at 0.5 GPa. This is 2.3 times higher than that of Ca₃Co₄O_9+δ (246 μW m^?1 K^?2). Nanostructure examinations show that the pellets pressed at 0.5 and 2 GPa have different nano-lamella structures. This work suggests that Yb is an effective doping element for enhancing the electrical transport properties of Ca₃Co₄O_9+δ, and the optimum doping level is related to the nanostructure of the bulk pellets.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Interfacial reactions of Ba2YCu3O6+z with coated conductor buffer layer,LaMnO3

Chemical interactions between the Ba₂YCu₃O_6+x superconductor and the LaMnO₃ buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba₂YCu₃O_6+x–LaMnO₃ system. The Ba₂YCu₃O_6+x–LaMnO₃ join within the BaO–(Y₂O₃–La₂O₃)–MnO₂–CuO_x multi-component system is non-binary. At 810 °C (p_O2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba_2?x(La_1+x?yY_y)Cu₃O_6+z, Ba(Y_2?xLa_x)CuO₅, (La_1?xY_x)MnO₃, (La,Y)Mn₂O₅. The crystal chemistry and crystallography of Ba(Y_2?xLa_x)CuO₅ and (La_1?xY_x)Mn₂O₅ were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y_2?xLa_x)CuO₅ are Ba(Y_1.8La_0.2)CuO₅ and Ba(Y_0.1La_1.9)CuO₅, respectively. The structure of Ba(Y_1.8La_0.2)CuO₅ is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å³, and D_x = 6.29 g cm^?3. YMn₂O₅ and LaMn₂O₅ do not form solid solution at 810 °C (p_O2 = 100 Pa) or at 950 °C (in air). The structure of YMn₂O₅ was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å³. A reference X-ray pattern was prepared for YMn₂O₅.     

A ceria layer as diffusion barrier between LAMOX and lanthanum strontium cobalt ferrite along with the impedance analysis

A thin interlayer of samarium doped ceria (SDC) is applied as diffusion barrier between La_1 ? xSr_xCo_yFe_1 ? yO₃ x = 0.1–0.4, y = 0.2–0.8 (LSCF) cathode and La_1.8Dy_0.2Mo_1.6W_0.4O₉ (LDMW82) electrolyte to obstruct Mo–Sr diffusion and solid state reaction in the intermediate temperature range of SOFC. We demonstrate the effectiveness of the diffusion barrier through contrasting the clearly defined interfaces of LSCF/SDC/LDMW82 against a rugged growing product layer of LSCF/LDMW82 in 800 °C thermal annealing, and analyze the product composition and the probable new phase. In addition, the measured polarization resistance is considerably lower for the half-cell with a diffusion barrier. Therefore, the electrochemical performance of the LSCF cathode is investigated on the SDC-protected LDMW82. The cell with LSCF (x = 0.4) persistently outperforms the one with x = 0.2 in polarization resistance because of its small low-frequency contribution. The activation energy of polarization resistance is also lower for La_0.6Sr_0.4Co_yFe_1 ? yO₃ (112–135 kJ/mol), than that for La_0.8Sr_0.2Co_yFe_1 ? yO₃ (156–164 kJ/mol). La_0.6Sr_0.4Co_yFe_1 ? yO₃ y = 0.4–0.8 is the proper composition for the cathode interfaced to SDC/LDMW82.     

Electric property of mixed conductor BaIn1−xCoxO3−δ

We synthesized BaIn_1−xCo_xO_3−δ (x = 0–0.8) with a defective perovskite structure by partly replacing In with Co in Ba₂In₂O₅. Based on XRD measurements, the synthesized compound was found to have cubic perovskite and orthorhombic brownmillerite structures depending on the amount of Co. BaIn_1−xCo_xO_3−δ (x = 0.2 and 0.3) showed high total electrical conductivities without undergoing the structural transformation that the original Ba₂In₂O₅ undergoes. Some of the samples showed both electronic and oxide ionic conductivities. At the same time, the oxide ionic conductivity was comparable with that of Ba₂In₂O₅. For example, the sample with x = 0.1 had a total electrical conductivity of 4.7 × 10^− 1 S cm^− 1 and an oxide ion transport number of 0.52 at 850 °C.     

Structural and electrochemical properties of LiNi0.5Mn0.5 − xAlxO2 (x = 0, 0.02, 0.05, 0.08, and 0.1) cathode materials for lithium-ion batteries

Layered LiNi_0.5Mn_0.5 ? xAl_xO₂ (x = 0, 0.02, 0.05, 0.08, and 0.1) series cathode materials for lithium-ion batteries were synthesized by a combination technique of co-precipitation and solid-state reaction, and the structural, morphological, and electrochemical properties were examined by XRD, FT-IR, XPS, SEM, CV, EIS, and charge–discharge tests. It is proven that the aliovalent substitution of Al for Mn promoted the formation of LiNi_0.5Mn_0.5 ? xAl_xO₂ structures and induced an increase in the average oxidation number of Ni, thereby leading to the shrinkage of the lattice volume. Among the LiNi_0.5Mn_0.5 ? xAl_xO₂ materials, the material with x = 0.05 shows the best cyclability and rate ability, with discharge capacities of 219, 169, 155, and 129 mAh g^? 1 at 10, 100, 200, and 400 mA g^? 1 current density respectively. Cycled under 40 mA g^? 1 in 2.8–4.6 V, LiNi_{0. 5}Mn_0.45Al_0.05O₂ shows the highest discharge capacity of about 199 mAh g^? 1 for the first cycle, and 179 mAh g^? 1 after 40 cycles, with a capacity retention of 90%. EIS analyses of the electrode materials at pristine state and state after first charge to 4.6 V indicate that the observed higher current rate capability of LiNi_{0. 5}Mn_0.45Al_0.05O₂ can be understood due to the better charge transfer kinetics.     

Hydrothermal synthesis of mesoporous Co3O4 nanobelts by means of a compound precursor

In the present work, high surface area mesoporous cobalt oxide (Co₃O₄) nanobelts have been synthesized by thermal treatment of cobalt hydroxide carbonate (CHC) precursors. CHC nanobelts were prepared by a facile hydrothermal method. Control experiments with variations in reaction time, solvent and different cobalt source revealed that temperature and sulfates are key factors in determining the formation of CHC nanobelts. Scanning electron microscopy and transmission electron microscopy images showed that the Co₃O₄ nanobelts consisted of mesoporous nanobelts with the average width of 40 nm. Brunauer–Emmett–Teller (BET) gas adsorption measurement further indicated that the products presented a rather large surface area (172.09 m² g^?1).     

An oxygen permeable membrane La0.8Sr0.2(Ga0.8Mg0.2)1 − xCrxO3 − δ for a reduced atmosphere

Mixed electron hole and oxide ion conducting perovskite-type oxides, La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ (0 ≤ x ≤ 1.0)_, were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ increases with increasing x. The oxygen permeation flux across the La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10^? 7 mol^? 1 cm^? 2 at 1100 °C in a oxygen activity gradient of air/10^? 2 Pa is observed in La_0.8Sr_0.2(Ga_0.8Mg_0.2)_0.6Cr_0.4O_3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10^? 10 Pa at 1000 °C.