DC conductivity and AC impedance of Mn doped magnesia alumina spinel (MgAl2-2xMn2xO4) over a large temperature range

MgAl_2-2xMn_2xO₄ (MAMO) with x = 0-0.12 was synthesized in a single-phase form by solid-state reaction. XRD analysis showed that the samples had the cubic center structure of the Fd-3 m space group. Electrical properties of the samples were studied over the temperature range of 300 K∼1073 K. The results showed that the DC conductivity (σ_DC) increased from 10⁻¹¹S/cm at 300 K (MAMO, x = 0) to 10^-3S/cm at 1073 K (MAMO, x = 0.12). The equivalent circuit of the complex impedance spectra suggested that the relaxation of charge carriers was of non-Debye type. The conduction was mainly caused by grain boundaries and the capacitance was mainly attributed to polarization. The complex permittivity values (ε’ and ε’’) were increased by two orders of magnitude with the increase in Mn content and temperature over the measured frequency range (1 Hz-1 MHz). Therefore, doping with Mn could be applied to modify the electrical properties of MAMO at high temperature.     

Accommodation of impurities in α-Al2O3, α-Cr2O3 and α-Fe2O3

Atomic scale computer simulation was used to predict the mechanisms and energies associated with the accommodation of aliovalent and isovalent dopants in three host oxides with the corundum structure. Here we consider a much more extensive range of dopant ions than has previously been the case. This enables a rigorous comparison of calculated mechanism energetics. From this we predict that divalent ions are charge compensated by oxygen vacancies and tetravalent ions by cation vacancies over the full range of dopant radii. When defect associations are included in the model these conclusions remain valid. At equilibrium, defects resulting from extrinsic dopant solution dominate intrinsic processes, except for the largest dopant cations. Solution reaction energies increase markedly with increasing dopant radius. The behaviour of cluster binding energies is more complex.     

Effects of complex doping on microstructural and electrical properties of PZT ceramics

The influence of complex dopants including donor and acceptor ions on microstructure and electrical properties of PZT (Zr/Ti = 53/47) ceramics was investigated. The prepared PZT ceramics modified with complex soft dopants, La⁺³ and Nb⁺⁵, showed that the piezoelectric properties were enhanced and stable with the compositional variations, which made it possible to establish the higher reliability and reproducibility of the piezoelectric performances. For 1.0 mol% La and 1.2 mol% Nb doped composition, the maximum value, k _P = 0.66, was obtained. Unlike single element doping, the complex doping of both the donor and acceptor ions caused various compensation effects for the piezoelectric properties of the PZT ceramics. The improved piezoelectric properties, i.e., enhanced Q _m with remaining higher k _p , were obtained in the PZT composition complexly doped with La⁺³ and Fe⁺³. For 1.0 mol% La and 2.0 mol% Fe doped PZT composition, relatively high Q _m and k _p values of 580 and 0.53, respectively, were obtained. It was also shown that the PZT composition had the rather lowered dielectric constant, ε _r = 800, and considerably low loss, tanδ = 0.003. By changing the dopants compositions, the properties can also be tailored over wider range.     

Low Temperature Water–Gas Shift/Methanol Steam Reforming: Alkali Doping to Facilitate the Scission of Formate and Methoxy C–H Bonds over Pt/ceria Catalyst

Doping Pt/ceria catalysts with the Group 1 alkali metals was found to lead to an important weakening of the C–H bond of formate and methoxy species. This was demonstrated by a shift to lower wavenumbers of the formate and methoxy ν(CH) vibrational modes by DRIFTS spectroscopy. Li and Na-doped Pt/ceria catalysts were tested relative to the undoped catalyst for low temperature water–gas shift and methanol steam reforming using a fixed bed reactor and exhibited higher catalytic activity. Steaming of formate and methoxy species pre-adsorbed on the catalyst surface during in-situ DRIFTS spectroscopy suggested that the species were more reactive for dehydrogenation steps in the catalytic cycle for the Li and Na-doped catalysts relative to undoped Pt/ceria. However, with increasing atomic number over the series of alkali-doped catalysts, the stability of a fraction of the carbonate species was found to increase. This was observed during TPD-MS measurements of the adsorbed CO₂ probe molecule by a systematic increase of a high temperature peak for a fraction of the CO₂ desorbed. This result indicates that alkali-doping is an optimization problem—that is, while improving the dehydrogenation rates of methoxy and formate species, the carbonate intermediate stability increases, making it difficult to liberate the CO₂. Infrared spectroscopy results of CO adsorbed on Pt and ceria suggest that the alkali dopant is located on, and electronically modifies, both the Pt and ceria components. The results not only lend further support to the role that methoxy and formate species play as intermediates in the catalytic mechanisms, but also provide a path forward for improving rates by means other than resorting to higher noble metal loadings.     

Grain boundary complexion and transparent polycrystalline alumina from an atomistic simulation perspective

Transparent alumina is often processed with sintering additives such as, Y, La, and Mg, in order to limit its grain growth at high sintering temperatures. Usually, these additives segregate to the grain boundaries due to their larger cationic size than Al and low solubility in bulk α-alumina. The grain boundary excess of these additives plays a key role in determining stable grain boundary complexions and thereby, the grain growth characteristics of the polycrystalline alumina. In the current work, the grain boundary segregation of trivalent (Y, La) as well as bivalent (Mg) dopants on several alumina grain boundaries was simulated using the force field based energy minimization method. Calculated segregation energy plots and atomistic structure analysis, for the case of trivalent dopants, suggest that there is a critical concentration (3–4 atoms/nm²) for achieving the lowest mobility monolayer grain boundary complexion. The bivalent dopant Mg plays a role in grain boundary complexion through creating ordered arrays of oxygen vacancies at the grain boundary and helps create the space for the easier occupation of the grain boundary cationic sites by the trivalent dopants in case of codoping. It was also observed that the twin grain boundaries are more preferable in comparison to general high angle grain boundaries to obtain monolayer complexions, which are necessary for limiting grain growth. The use of atomistic simulations can thus guide the experimentalist towards optimum dopant concentrations to better control ceramic microstructures. In a more general sense the possibility of second phase formation or an incipient second phase for high grain boundary concentrations >8 cations/nm² is briefly discussed.     

The effect of multiple doping on electrical conductivity of gadolinia-doped ceria electrolyte

Combinations of two or four trivalent oxides were substituted for gadolinia up to 5 mol% in the 20 mol% gadolinia-doped ceria electrolyte as additional dopants. Most of them increased the electrical conductivity of the electrolyte but some did not. Among them (YLa)_0.01Gd_0.19Ce_0.8O_1.9 and (YSm)_0.03Gd_0.17Ce_0.8O_1.9 showed the highest electrical conductivities, respectively, at 800 ‡C and 600 ‡C. These experimental results were analyzed in terms of activation enthalpy and entropy for ionic conduction. Among the various possible contributions to the activation entropy, only the configurational entropy was taken into account for the explanation.     

First-principles rational design of M-doped LiBH4(010) surface for hydrogen release: Role of strain and dopants (M=Na,K, Al,F, or Cl)

To overcome the important challenges of facilitating dehydrogenation in the complex metal hydride, LiBH₄, the structural and chemical effects were considered using the strain (−3% − +3%) and five dopants (M = Na, K, Al, F, or Cl). The desorption energies of a hydrogen molecule decreased with increasing tensile strain on the LiBH₄(010) surface. The tensile strain was useful for promoting the dehydrogenation process by weakening the B-H interactions. Among the dopants examined, the most favorable dopant to enhance dehydrogenation was Al. The ranking of dopants for hydrogen release was Al > Cl > F > Na > K. Remarkably, codoping of Al and Cl was more effective for hydrogen release than the single doping of Al or Cl with the lowest hydrogen desorption energy. These methods that destabilize metal hydrides are practical for tuning the hydrogen release of LiBH₄ hydrides. These studies will provide efficient means for designing excellent hydrides for hydrogen release.     

Fluorescence and Phosphorescence in Organic Materials

Progress reports are a new type of article in Advanced Materials, dealing with the hottest current topics, and providing readers with a critically selected overview of important progress in these fields. It is not intended that the articles be comprehensive, but rather insightful, selective, critical, opinionated, and even visionary. We have approached scientists we believe are at the very forefront of these fields to contribute the articles, which will appear on an annual basis. The article below describes the latest advances in fluorescence and phosphorescence in organic materials.     

Roles of titanium dioxide and ion-doped titanium dioxide on photocatalytic degradation of organic pollutants (phenolic compounds and dyes) in aqueous solutions: A review

Water pollution by organic pollutants is an ever increasing problem for the global concerns. This paper presents a critical review on the abatement of organic pollutants, dyes and phenolic compounds in particular, using photocatalytic reaction by titanium dioxide (TiO₂). Mechanism of photocatalytic reaction is briefly discussed. A detailed search of published reports on the advancement in photocatalytic degradation of organic pollutants in wastewater by doping titanium dioxide with foreign species such as metal and non-metal component has also been carried out and analyzed in this paper.     

Processing and properties of luminescent Cr3+ doped transparent alumina ceramics

Transparent Cr₂O₃-doped alumina ceramics were prepared by slip casting, followed by pre-sintering in ambient atmosphere and hot isostatic pressing. The effect of dopant concentration on material properties, including microstructure and optical properties was evaluated. Real in-line transmittance in the range of 20–44 % was measured for the ceramics with the mean grain size <520 nm: the transmittance decreased with increasing grain size and Cr content. The excitation spectra consisted of two broad bands with maxima at 404 nm and 558 nm, corresponding to ⁴A_2g → ⁴T_1g and ⁴A_2g → ⁴T_2g transitions of Cr³⁺ ions in octahedral sites of α-Al₂O₃. The intensive deep red narrow emissions under violet/green light excitation, R-lines (²E_g → ⁴A_2g transition), were observed at 692.5 nm and 693.8 nm, that are very close to ruby single crystal. The highest emission was achieved at the Cr³⁺ concentration of 0.4 at.%. The luminescence decay curves exhibited single-exponential behaviour with decay times of ∼3.6 ms.