The Effect of Inhomogeneous Phase on the Critical Temperature of Smart Meta-superconductor MgB<Subscript>2</Subscript>

The critical temperature (T_C) of MgB₂, one of the key factors limiting its application, is highly desired to be improved. On the basis of the meta-material structure, we prepared a smart meta-superconductor structure consisting of MgB₂ micro-particles and inhomogeneous phases by an ex situ process. The effect of inhomogeneous phase on the T_C of smart meta-superconductor MgB₂ was investigated. Results showed that the onset temperature (\(T_{\mathrm {C}}^{\text {on}}\)) of doping samples was lower than those of pure MgB₂. However, the offset temperature (\({T}_{\mathrm {C}}^{\text {off}}\)) of the sample doped with Y₂O₃:Eu³⁺ nanosheets with a thickness of 2 ～ 3 nm which is much less than the coherence length of MgB₂ is 1.2 K higher than that of pure MgB₂. The effect of the applied electric field on the T_C of the sample was also studied. Results indicated that with the increase of current, \({T}_{\mathrm {C}}^{\text {on}}\) is slightly increased in the samples doping with different inhomogeneous phases. With increasing current, the \({T}_{\mathrm {C}}^{\text {off}}\) of the samples doped with nonluminous inhomogeneous phases was decreased. However, the \({T}_{\mathrm {C}}^{\text {off}}\) of the luminescent inhomogeneous phase doping samples increased and then decreased with increasing current.     

Electrochemical impedance studies of capacity fading of electrodeposited ZnO conversion anodes in Li-ion battery

Electrodeposited ZnO coatings suffer severe capacity fading when used as conversion anodes in sealed Li cells. Capacity fading is attributed to (i) the large charge transfer resistance, \(R_{\mathrm{ct}}\) (300–700 \(\Omega \)) and (ii) the low \(\hbox {Li}^{+}\) ion diffusion coefficient, \(D_{\mathrm{Li}}^{+}\ (10^{-15}\) to \(10^{-13}\hbox { cm}^{2}\hbox { s}^{-1})\). The measured value of \(R_{\mathrm{ct}}\) is nearly 10 times higher and \(D_{\mathrm{Li}}^{+}\) 10–100 times lower than the corresponding values for \(\hbox {Cu}_{2}\hbox {O}\), which delivers a stable reversible capacity.     

Effect of Ti-ion non-stoichiometry on microstructure and microwave dielectric characteristic of Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> ceramics

This paper studies the microwave dielectric properties, microstructure, vibration and densification of Li₂ZnTi_3+xO_8+2x (\(- 0.04 \le {\text{x}} \le +0.06\)) ceramics, manufactured via a conventional mixed oxide route. The X-ray diffraction and Raman spectroscopy revealed the unit cell parameter and cation ordering in LZT non-stoichiometry in their vibrational modes. The densification and phase composition were characterized by the EDX and SEM methods. It was found that a slight Ti vacancy can improve the relative density to the maximum value (96.2%). The XRD results showed that the second phase of TiO₂ in the Li₂ZnTi_3.06O_8.12 composition is formed. The sintered samples were detected in the microwave frequency range by using the resonance technique. The \({\text{~}}{\tau _f}\) values of the ceramics within Ti excess adjusted to near zero. The Li₂ZnTi_2.96O_7.92 ceramic showed the best relative density, single phase and best microwave dielectric \({\varepsilon _r}~={\text{ }}25.98\), Q?×?f?=?61,000 GHz, \({\tau _f}={\text{ }} - 17.4{\text{ ppm/}}^\circ {\text{C}}\) sintered at 1100 °C for 4 h.     

Effects of electrolyte concentration and current density on the properties of electro-deposited NiFeW alloy coatings

NiWP alloy coatings were prepared by electrodeposition, and the effects of ferrous chloride (\(\hbox {FeCl}_{2})\), sodium tungstate (\(\hbox {Na}_{2}\hbox {WO}_{4})\) and current density (\(D_{\mathrm{K}}\)) on the properties of the coatings were studied. The results show that upon increasing the concentration of \(\hbox {FeCl}_{2}\), initially the Fe content of the coating increased and then tended to be stable; the deposition rate and microhardness of coating decreased when the cathodic current efficiency (\(\eta \)) initially increased and then decreased; and for a \(\hbox {FeCl}_{2}\) concentration of \(3.6\, \hbox {g\,l}^{-1}\), the cathodic current efficiency reached its maximum of 74.23%. Upon increasing the concentration of \(\hbox {Na}_{2}\hbox {WO}_{4}\), the W content and microhardness of the coatings increased; the deposition rate and the cathode current efficiency initially increased and then decreased. The cathodic current efficiency reached the maximum value of 70.33% with a \(\hbox {Na}_{2}\hbox {WO}_{4}\) concentration of 50 g \(\hbox {l}^{-1}\), whereas the deposition rate is maximum at 8.67 \(\upmu \hbox {m}\,\hbox {h}^{-1}\) with a \(\hbox {Na}_{2}\hbox {WO}_{4}\) concentration of \(40\, \hbox {g\,l}^{-1}\). Upon increasing the \(D_{\mathrm{K}}\), the deposition rate, microhardness, Fe and W content of the coatings increased, the cathodic current efficiency increases first increased and then decreased. When \(D_{\mathrm{K}}\) was 4 A dm\(^{-2}\), the current efficiency reached the maximum of 73.64%.     

Short-range antiferromagnetic correlations and large magnetic entropy change in (La<Subscript>0.5</Subscript>Pr<Subscript>0.5</Subscript>)<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>

We report a detailed study of magnetic properties in manganite (La_0.5Pr_0.5)_0.67Ca_0.33MnO₃. In contrast to the usual beliefs, it shows an abnormal upturn deviation from the Curie–Weiss law on the inverse susceptibility curve. Such a non-Griffiths-like phase is further confirmed from the inverse double integrated intensities of electron paramagnetic resonance spectrum. Because La\(^{3+}\) ions are substituted by Pr\(^{3+}\) ions with 50% concentrations, the ratio of three ions (La\(^{3+}\), Pr\(^{3+}\), Ca\(^{2+}\)) is close to 1 on A-site sublattice. As a result, some short-range antiferromagnetic (CO AFM) phases come into being in the system due to the existence of localized charge ordering states. Therefore, the upturn deviation from Curie–Weiss law originates from the appearance of short-range CO AFM correlations above \(T_{\text{C}}\). Additionally, a magnetic field-driven-metamagnetic transition is found, which gives a main contribution for the large magnetic entropy change (MEC) observed in this sample. Both the Arrott plot and the renormalized MEC curves testify that this transition belongs to first-order magnetic transition. The insignificant hysteresis loop indicate that the inevitable thermal hysteresis can be ignored in the present first-order material implying that it is a potential candidate for the cryogenic temperature magnetic refrigeration.     

Superconducting Properties of NdO<Subscript>0.5</Subscript><Emphasis Type="Bold">F</Emphasis><Subscript>0.5</Subscript>BiS<Subscript>2</Subscript> Single Crystals

We report on superconducting properties of high-quality single crystals of F-substituted NdOBiS₂ using low-temperature magnetization and transport measurements. Using the mixture of CsCl and KCl as the flux, we have synthesized our single crystals. This compound exhibits bulk superconductivity with a transition temperature of about T _c～4.6 K. The critical current density J _c as a function of temperature has been derived and decreases with the increasing temperature. We construct the phase diagram H _c2(T). The zero-temperature value for \(H_{\mathrm {c2}}^{B\parallel c}\) for value for \(T_{c}^{90~\%}\) and \(T_{c}^{0~\%}\) is estimated to be approximately 2.17 and 1.72 T respectively by using Werthamer-Helfand-Hohenberg model.     

Computational investigations of Cu-embedded MoS<Subscript>2</Subscript> sheet for CO oxidation catalysis

Elevated amount of CO levels in the atmosphere poses serious health and environmental hazards. Oxidation of CO using suitable catalysts is one of the methods to control it. By means of DFT calculations, single Cu atom doped in S vacancy of MoS₂ nanosheet is studied for CO oxidation catalysis. Cu atom is strongly confined at the S-defective site of the MoS₂ sheet, possessing high energy barrier for the diffusion to its neighboring sites. Adsorption energy, charge transfer and orbital hybridization of CO and O₂ molecules adsorbed Cu-doped MoS₂ sheet reveal that O₂ is relatively more strongly adsorbed than CO. High adsorption energy of O₂ (??2.115 eV) and large charge transfer between O₂ and Cu–MoS₂ sheet (0.493e), compared to CO, make O₂ adsorption more favorable, which extenuates CO poisoning and hence helps in the efficient CO oxidation process. The complete oxidation of CO takes place in two steps: \( {\text{CO}} + {\text{O}}_{2} \to {\text{OOCO}} \) with activation energy of 0.201 eV, succeeded by \( {\text{OOCO}} + {\text{CO}} \to 2{\text{CO}}_{2} \) without any energy barrier. Our results show that the basal plane of MoS₂ sheet gets activated by embedding it with Cu metal, which can catalyze CO oxidation reaction effectively and without poisoning issues. The high activity, stability and low cost features can possibly encourage fabricating MoS₂-based catalysts for CO oxidation reaction.     

Reactionary processes during mechanical treatment of mixtures of ZnO and MnO<Subscript>2</Subscript>. I. Formation of defects and solid solution

Kinetics of defects formation, reaction process and formation of solid solution in powder mixtures of ZnO and MnO₂ induced by prolonged mechanical treatment (MT) have been investigated (X-ray, FTIR, EPR). At MT in zones of deformation-destruction the different defects (\( {\text{V}}_{{\text{Zn}}}^ - :{\text{Zn}}_{\text{i}}^{\text{0}} \) (I), \( {\text{V}}_{{\text{Zn}}}^ - \) (II), and \( {\text{(V}}_{{\text{Zn}}}^ - {\text{)}}_{\text{2}}^ - \) (III) centers at all) are forming. The defects have various physical and chemical properties, and have different activation energies of annealing, E_act The part of these defects is responsible for the processes of hydration and carbonation of samples. In turn, the formation of defects is accompanied by development of various mechanothermical processes, which increase temperature of the sample, T _MT, with the increasing of duration of MT, t _MT. The increasing of t _MT activates the reactionary processes: promotes a consecutive annealing the «low-temperature» defects having small values of E_act (I, II and III) and also leads to formation of Mn²⁺-doped Zn(OH)₂. With the further increase of t _MT, the process of MT is accompanied by an increasing of temperature of samples up to equilibrium, T _eq and accumulation of “high-temperature” defects in the sample. As a result, in the sample the conditions for intensification of volumetric diffusion processes and formation of Mn²⁺-doped ZnO were created.     

Microstructure and Magnetic Properties of Sn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> Thin Films Prepared by Flash Evaporation Technique

An effort was made to develop semiconductor oxide-based room temperature dilute magnetic semiconductor (DMS) thin films based on wide band gap and transparent host lattice with transition metal substitution. The Sn\(_{\mathrm {1}-x}\)Ni\(_{x}\textit {O}_{\mathrm {2}}\) (\(x\,= \mathrm {0.00, 0.03, 0.05, 0.07, 0.10, and \,0.15}\)) thin film samples were prepared on glass substrates by flash evaporation technique. All the samples were shown single phase crystalline rutile structure of host SnO\(_{\mathrm {2}}\) with dominant (110) orientation. The Ni substitution promotes reduction of average crystallite size in SnO\(_{\mathrm {2}}\) as evidenced from the reduction of crystallite size from 40 (SnO\(_{\mathrm {2}}\)) to 20 nm (Sn\(_{\mathrm {0.85}}\)Ni\(_{\mathrm {0.15}}\textit {O}_{\mathrm {2}}\)). In the energy dispersive spectra as well as X-ray photoelectron spectra of all the samples show, the chemical compositions are close to stoichiometric with noticeable oxygen deficiency. The crystalline films were formed by coalescence of oval-shaped polycrystalline particles of 100 nm size as evidenced from the electron micrographs. The energy band gap of DMS films decreases from 4 (SnO\(_{\mathrm {2}}\)) to 3.8 eV (x \(=\) 0.05) with increase of Ni content. The magnetic hysteresis loops of all the samples at room temperature show soft ferromagnetic nature except for SnO\(_{\mathrm {2}}\) film. The SnO\(_{\mathrm {2}}\) films show diamagnetic nature and it converts into ferromagnetic upon substitution of 3 % Sn\(^{\mathrm {4+}}\) by Ni\(^{\mathrm {2+}}\). The robust intrinsic ferromagnetism (saturation magnetization, 21 emu/cm\(^{\mathrm {3}}\)). Further increase of Ni content weakens ferromagnetic strength due to Ni-O antiferromagnetic interactions among the nearest neighbour Ni ions via O\(^{\mathrm {2-}}\) ions. The observed magnetic properties were best described by bound magnetic polarons model.     

Thermodynamic Properties at Saturation Derived from Experimental Two-Phase Isochoric Heat Capacity of 1-Hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

New measurements are reported for the isochoric heat capacity of the ionic liquid substance 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C6mim][NTf2]). These measurements extend the ranges of our earlier study (Polikhronidi et al. in Phys Chem Liq 52:657, 2014) by 5 % of the compressed liquid density and by 75 K. An adiabatic calorimeter was used to measure one-phase \((C_{\mathrm{V1}})\) liquid and two-phase \((C_{\mathrm{V2}})\) liquid + vapor isochoric heat capacities, densities \((\rho _s)\), and phase-transition temperatures \((T_s)\) of the ionic liquid (IL) substance. The combined expanded uncertainty of the density \(\rho \) and isochoric heat capacity \(C_\mathrm{V}\) measurements at the 95 % confidence level with a coverage factor of \(k = 2\) is estimated to be 0.15 % and 3 %, respectively. Measurements are concentrated in the immediate vicinity of the liquid + vapor phase-transition curve, in order to closely observe phase transitions. The present measurements and those of our earlier study are analyzed together and are presented in terms of thermodynamic properties \((T_s\), \(\rho _s\), \(C_{\mathrm{V1}}\) and \(C_{\mathrm{V2}})\) evaluated at saturation and in terms of key-derived thermodynamic properties \(C_\mathrm{P}\), \(C_\mathrm{S}\), \(W_\mathrm{S}^{{\prime }}\), \(K_{\mathrm{TS}}^{{\prime }}\), \(\left( {\partial P/\partial T} \right) _{\mathrm{V}}^{\prime }\), and \(\left( {\partial V/\partial T} \right) _\mathbf{P}^{\prime })\) on the liquid + vapor phase-transition curve. A thermodynamic relation by Yang and Yang is used to confirm the internal consistency of measured two-phase heat capacities \(C_{\mathrm{V2}} \), which are observed to fall perfectly on a line as a function of specific volume at a constant temperature. The observed linear behavior is exploited to evaluate contributions to the quantity \(C_{\mathrm{V2}} = f(V, T)\) from chemical potential \(C_{{\mathrm{V}\upmu }} =-T\frac{\mathrm{d}^{{2}}\mu }{\mathrm{d}T^{2}}\) and from vapor pressure \(C_{\mathrm{VP}} =VT\frac{\mathrm{d}^{2}P_{\mathrm{S}} }{\mathrm{d}T^{2}}\). The physical nature and specific details of the temperature and specific volume dependence of the two-phase isochoric heat capacity and some features of the other derived thermodynamic properties of IL at liquid saturation curve are considered in detail.     

High-pressure studies of superconductivity in $$\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}$$

\(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\) crystallizes in tetragonal CeOBiS\(_{2}\) structure (S. G. P4/nmm). We have investigated the effect of pressure on magnetization measurements. Our studies suggest improved superconducting properties in polycrystalline samples of \(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\). The \(T_{\mathrm{c}}\) in our sample is 5.3 K, at ambient pressure, which is marginal but definite enhancement over \(T_{\mathrm{c}}\) reported earlier (= 5.1 K). The upper critical field \(H_{\mathrm{c}2}\)(0) is greater than 3 T, which is higher than earlier report on this material. As determined from the M–H curve, both \(H_{\mathrm{c}2}\) and \(H_{\mathrm{c}1}\) decrease under external pressure P (0 \(\le P \le \) 1 GPa). We observe a decrease in critical current density and transition temperature on applying pressure in \(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\).     

Physical,optical and structural studies of copper-doped lead oxychloro borate glasses

Bluish coloured glasses are obtained from the composition PbCl\(_{2}\)–PbO–B\(_{2}\)O\(_{3}\) doped with Cu\(^{2+}\) ions. Basic physical properties and spectroscopic studies (optical absorption, electron paramagnetic resonance, Fourier transform infrared and Raman spectroscopies) were carried out on these samples. The increase in PbCl\(_{2}\) content resulted in the decrease in density and increase in molar volume. At optical frequencies, band gaps and Urbach energies were evaluated and their variation is explained. Spin-Hamiltonian parameters (SHP) obtained from the EPR spectra suggest that the ligand environment around Cu\(^{2+}\) is tetragonally distorted octahedral sites and the orbital \(d_{x^{2}-{y}^{2}} \) is the ground state. The characteristics broad bands in the optical absorption spectra are assigned to the \(^{2}\)B\(_{\mathrm{1g}}\,\rightarrow \, {}^{2}\)B\(_{\mathrm{2g}}\) transition. The bonding coefficient values were evaluated using optical data and SHP. FTIR studies suggested that the glass structure is built up of BO\(_{3}\) and BO\(_{4}\) units. The presence of diborate, pyroborate, pentaborate groups, etc. in the glass network was confirmed from Raman spectra.     

Structural,magnetic and photocatalytic characterization of Bi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript> nanoparticles synthesized by thermal decomposition method

Single-phase La-substituted bismuth ferrite (Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\)) nanoparticles have been synthesized by thermal decomposition of a glyoxylate precursor. The crystal structure transition of BiFeO\(_{\mathbf {3}}\) from the rhombohedral (R3c) to the cubic \(\boldsymbol {Pm}\bar {\mathbf {3}}\boldsymbol {m}\) structure by La addition was confirmed by X-ray diffraction and infrared spectrometry methods. Furthermore, the Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles showed a weak ferrimagnetism behaviour, while the magnetization increased from 0.18 to 0.48 emu g\(^{\mathbf {-1}}\) with La substitution. The Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles exhibited strong absorption in the visible region with the optical band gap calculated from Tauc’s plot in the range of 2.19–2.15 eV. Furthermore, the effects of La substitution on the photodegradation of the methylene blue (MB) under visible light were also studied. The photodegradation of MB dye was enhanced from 64 to \(\sim \)99% with increasing La substitution from \(\boldsymbol {x =}\) 0 to 0.1 and then decreased to 8% for \(\boldsymbol {x =}\) 0.15.     

Effect of the Interfacial Disorder on the Magnetotransport Properties in Ni<Subscript>81</Subscript>Fe<Subscript>19</Subscript>/Ti<Subscript>10</Subscript><Emphasis Type="Italic">W</Emphasis><Subscript>90</Subscript> Multilayers

This work is a study of the interface structure effect on the magnetotransport properties in Ni₈₁Fe₁₉/Ti₁₀ W ₉₀ magnetic multilayer. The overall weakness showed by experimental magnetoresistance rate \(\text {MR}_{\exp }\) is probably due to a degradation of the interface quality caused by the apparition of a disordered phase NiFeW at the interface. Thus, we propose in this paper an extension to the Johnson-Camley semi classical model that takes in consideration the evolution of the interface structure, which makes it possible to reproduce quite faithfully the experimental results \(\text {MR}_{\exp } (t_{\text {NiFe}})\) for all ranges of magnetic layer thicknesses, confirming the important role of the interface structure on the electronic transport properties.     

Thermal Conductivity of Pyroclastic Soil (<Emphasis Type="BoldItalic">Pozzolana</Emphasis>) from the Environs of Rome

The paper reveals the experimental procedure and thermo-physical characteristics of a coarse pyroclastic soil (Pozzolana), from the neighborhoods of Rome, Italy. The tested samples are comprised of 70.7 % sand, 25.9 % silt, and 3.4 % clay. Their mineral composition contained 38 % pyroxene, 33 % analcime, 20 % leucite, 6 % illite/muscovite, 3 % magnetite, and no quartz content was noted. The effective thermal conductivity of minerals was assessed to be about \(2.14\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\). A transient thermal probe method was applied to measure the thermal conductivity (\(\lambda \)) over a full range of the degree of saturation \((S_{\mathrm{r}})\), at two porosities (n) of 0.44 and 0.50, and at room temperature of about \(25\,^{\circ }\hbox {C}\). The \(\lambda \) data obtained were consistent between tests and showed an increasing trend with increasing \(S_{\mathrm{r}}\) and decreasing n. At full saturation (\(S_{\mathrm{r}}=1\)), a nearly quintuple \(\lambda \) increase was observed with respect to full dryness (\(S_{\mathrm{r}}=0\)). In general, the measured data closely followed the natural trend of \(\lambda \) versus \(S_{\mathrm{r}}\) exhibited by published data at room temperature for other unsaturated soils and sands. The measured \(\lambda \) data had an average root-mean-squared error (RMSE) of \(0.007\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\) and \(0.008\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\) for n of 0.50 and 0.44, respectively, as well as an average relative standard deviation of the mean at the 95 % confidence level \((\hbox {RSDM}_{0.95})\) of 2.21 % and 2.72  % for n of 0.50 and 0.44, respectively.     

Evolution of magnetic structure of Dy(Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>B<Subscript>2</Subscript>C

DyNi\(_{2}\)B\(_{2}\)C superconducts at \(T_{c} \approx 6\,{\text{K}}\) and orders antiferromagnetically at \(T_{N}\approx 10\,{\text{K}}.\) Its non-superconducting isomorph DyCo\(_{2}\)B\(_{2}\)C is a ferromagnet with \(T_{C}\approx 6\,{\text{K}}.\) With the aim of mapping out the magnetic properties, in particular magnetic structures, of their solid solutions, we synthesized \(^{11}\)B-enriched Dy(Co\(_{x}\)Ni\(_{1-x}\))\(_{2}\)B\(_{2}\)C (\(x=0.2,0.4,0.6,0.8\)). We investigated the evolution of their magnetic, thermal and transport properties by means of the magnetization, resistivity, specific heat and neutron diffraction techniques. Their crystal structures were confirmed to be ThCr\(_{2}\)-Si\(_{2}\)-type tetragonal (I4/mmm) phase. The magnetic structure was found to be antiferromagnetic with k_0.2 = (0, 0, 1) for x = 0.2; helicoidal with k\(_{0.4}\) = (0, 0, 0.49) and k\(_{0.6}\) = (0, 0, 0.46) for, respectively, x = 0.4 and 0.6 and ferromagnetic with k\(_{0.8}\) = (0, 0, 0) for x = 0.8. We discuss the evolution of such magnetic modes assuming a scenario of an idealized one-dimensional chain of transverse magnetic moments.     

Electrocatalytic applications of platinum-decorated TiO<Subscript>2</Subscript> nanotubes prepared by a fully wet-chemical synthesis

Pt-decorated \(\hbox {TiO}_{2}\) nanotubes Pt@TiO₂ are prepared only by applying a set of facile wet-chemical redox reactions to ion track-etched polycarbonate templates. First, a homogeneous layer of Pt nanoparticles is deposited onto the complex template surface by reducing potassium tetrachloroplatinate with absorbed dimethylaminoborane. Second, the template is coated with a conformal \(\hbox {TiO}_{2}\) layer, using a chemical bath deposition reaction based on titanium(III) chloride. After the removal of the template, the rutile-type \(\hbox {TiO}_{2}\) nanotubes remain decorated with Pt nanoparticles and nanoparticle-clusters on their outside. During the process, neither vacuum techniques nor external current sources or addition of heat are employed. The crystallinity, composition, and morphology of the composite nanotubes are analysed by X-ray diffraction, scanning and transmission electron microscopy as well as by energy-dispersive X-ray spectroscopy. Finally, the obtained materials are examplarily applied in the electrooxidation of ethanol and formic acid, and their performances have been evaluated. Compared to conventional carbon black-supported Pt nanoparticles, the Pt@TiO₂ nanotubes show higher reaction rates. Mass activities of 2.36 \(\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}\) are reached in ethanol oxidation and 7.56 \(\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}\) in the formic acid oxidation. The present structures are able to exploit the synergy of Pt and \(\hbox {TiO}_{2}\) with a bifunctional mechanism to result in powerful but easy-to-fabricate catalyst structures. They represent an easily producible type of composite nanostructures which can be applied in various fields such as in catalytics and sensor technology.     

Effect of Zr Addition on Bi<Subscript>1.8</Subscript>Pb<Subscript>0.4</Subscript>Sr<Subscript>2.0</Subscript>Ca<Subscript>1.1</Subscript>Cu<Subscript>2.1</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Superconductor

The polycrystalline Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1 M_xO _y , with M = Zr (x = 0.0, 0.02, 0.04), were synthesized by solid-state reaction method and studied by X-ray diffraction analysis (XRD), scanning electron microscopy equipped with energy dispersive of X-ray analysis (SEM/EDX) and resistivity versus temperature measurements. The influence of the Zr addition on the Tc and microstructure properties of the superconducting compounds has been studied. SEM observations show whiskers grains randomly distributed and microstructural change due to the addition of Zr. The ZrO₂ was incorporated into the crystalline structure of BSCCO system in all samples. The crystallographic structure remains in a tetragonal form where a= b≠c. Generally, all samples exhibit semiconductor behaviour above \(T_{\mathrm {c}}^{\text {onset}}\). The onset critical temperature \(T_{\mathrm {c}}^{\text {onset}}\) increases up to 86 with x = 0.02. There is an enhancement in the critical temperature for doped samples as compared with pure Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1O _y .Changes in superconducting properties of ZrO₂ nanoparticle added Bi-2212 system were discussed.     

Temperature effects on the electrical characteristics of $$\mathrm{Al}/\mathrm{PTh}-\mathrm{SiO}_{2}/\mathrm{p\hbox {-}Si}$$ structure

The temperature-dependent current–voltage (\(I\text {--}V\)) and capacitance–voltage (\(C\text {--}V\)) characteristics of the fabricated Al/p-Si Schottky diodes with the polythiopene–SiO\(_{2}\) nanocomposite (\(\hbox {PTh--SiO}_{2}\)) interlayer were investigated. The ideality factor of \(\hbox {Al}/\hbox {PTh--SiO}_{2}/{p}\text {-Si}\) Schottky diodes has decreased with increasing temperature and the barrier height has increased with increasing temperature. The change in the barrier height and ideality factor values with temperature was attributed to inhomogeneties of the zero-bias barrier height. Richardson plot has exhibited curved behaviour due to temperature dependence of barrier height. The activation energy and effective Richardson constant were calculated as 0.16 eV and \(1.79 \times 10^{-8} \hbox {A\,cm}^{-2} \,\hbox {K}^{-2}\) from linear part of Richardson plots, respectively. The barrier height values determined from capacitance–voltage–temperature (\(C\text {--}V\text {--}T\)) measurements decrease with increasing temperature on the contrary of barrier height values obtained from \(I\text {--}V\text {--}T\) measurements.     

Influence of $$\hbox {TiO}_{2}$$ particle size and conductivity of the CuCrO$$_{2}$$2 nanoparticles on the performance of solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells have been fabricated with mesoporous \(\hbox {TiO}_{2 }\) photoanode and N719 dye as photosensitizer. First, \(\hbox {TiO}_{2}\) and non-doped, Zn- and Mg-doped CuCrO\(_{2}\) nanoparticles have been synthesized by sol–gel method. In addition, the \(\hbox {TiO}_{2}\) pastes have been prepared through Pechini-type sol–gel method. The effect of \(\hbox {TiO}_{2}\) particle size, mesoporous \(\hbox {TiO}_{2}\) photoanode thickness and solid-state electrolyte thickness on the efficiency of the fabricated devices has been investigated. Our results show that in spite of the low amount of dye loading for photoanode with large \(\hbox {TiO}_{2}\) nanoparticles (80–180 nm), the dye-sensitized solar cell made from it has higher efficiency than that constructed from the photoanode comprising of small particles about 10–15 nm in size. The higher efficiency is attributed to the longer diffusion length of electrons because of a better electron transport and penetration of a large amount of \(\hbox {CuCrO}_{2 }\) nanoparticles in the porous structure of \(\hbox {TiO}_{2}\) photoanode. By using the doped \(\hbox {CuCrO}_{2}\) nanoparticles, the efficiency has been increased from 0.027% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\) to 0.033% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Zn and further increased to 0.042% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Mg. The efficiency enhancement by doping is ascribed to the conductivity improvement due to the presence of impurity atoms.