Synthesis, structure, chemical stability, and electrical properties of Nb-, Zr-, and Nb-codoped BaCeO3 perovskites.

We report the effect of donor-doped perovskite-type BaCeO(3) on the chemical stability in CO(2) and boiling H(2)O and electrical transport properties in various gas atmospheres that include ambient air, N(2), H(2), and wet and dry H(2). Formation of perovskite-like BaCe(1-x)Nb(x)O(3±Î´) and BaCe(0.9-x)Zr(x)Nb(0.1)O(3±Î´) (x = 0.1; 0.2) was confirmed using powder X-ray diffraction (XRD) and electron diffraction (ED). The lattice constant was found to decrease with increasing Nb in BaCe(1-x)Nb(x)O(3±Î´), which is consistent with Shannon's ionic radius trend. Like BaCeO(3), BaCe(1-x)Nb(x)O(3±Î´) was found to be chemically unstable in 50% CO(2) at 700 °C, while Zr doping for Ce improves the structural stability of BaCe(1-x)Nb(x)O(3±Î´). AC impedance spectroscopy was used to estimate electrical conductivity, and it was found to vary with the atmospheric conditions and showed mixed ionic and electronic conduction in H(2)-containing atmosphere. Arrhenius-like behavior was observed for BaCe(0.9-x)Zr(x)Nb(0.1)O(3±Î´) at 400-700 °C, while Zr-free BaCe(1-x)Nb(x)O(3±Î´) exhibits non-Arrhenius behavior at the same temperature range. Among the perovskite-type oxides investigated in the present work, BaCe(0.8)Zr(0.1)Nb(0.1)O(3±Î´) showed the highest bulk electrical conductivity of 1.3 × 10(-3) S cm(-1) in wet H(2) at 500 °C, which is comparable to CO(2) and H(2)O unstable high-temperature Y-doped BaCeO(3) proton conductors.

In-situ powder X-ray diffraction investigation of reaction pathways for the BaCO(3)-CeO(2)-In(2)O(3) and CeO(2)-In(2)O(3) systems.

We report the first in-situ powder X-ray diffraction (PXRD) study of the BaCO(3)-CeO(2)-In(2)O(3) and CeO(2)-In(2)O(3) systems in air over a wide range of temperature between 25 and 1200 degrees C. Herein, we are investigating the formation pathway and chemical stability of perovskite-type BaCe(1-x)In(x)O(3-delta) (x = 0.1, 0.2, and 0.3) and corresponding fluorite-type Ce(1-x)In(x)O(2-delta) phases. The potential direct solid state reaction between CeO(2) and In(2)O(3) for the formation of indium-doped fluorite-type phase is not observed even up to 1200 degrees C in air. The formation of the BaCe(1-x)In(x)O(3-delta) perovskite structures was investigated and rationalized using in-situ PXRD. Furthermore the decomposition of the indium-doped perovskites in CO(2) is followed using high temperature diffraction and provides insights into the reaction pathway as well as the thermal stability of the Ce(1-x)In(x)O(3-delta) system. In CO(2) flow, BaCe(1-x)In(x)O(3-delta) decomposes above T = 600 degrees C into BaCO(3) and Ce(1-x)In(x)O(2-delta). Furthermore, for the first time, the in-situ PXRD confirmed that Ce(1-x)In(x)O(2-delta) decomposes above 800 degrees C and supported the previously claimed metastability. The maximum In-doping level for CeO(2) has been determined using PXRD. The lattice constant of the fluorite-type structure Ce(1-x)In(x)O(2-delta) follows the Shannon ionic radii trend, and crystalline domain sizes were found to be dependent on indium concentration.

Electrical transport properties of In-doped Ce(1-x)In(x)O(2-delta) (x = 0.1; 0.2).

We report the synthesis and electrical conductivity of fluorite-type Ce(1-x)In(x)O(2-delta) (x = 0.1; 0.2) in air, dry Ar, N(2) and H(2) in the temperature range of 300-800 degrees C. We have employed a new CO(2) capture technique to prepare the "metastable" fluorite-related structure Ce(1-x)In(x)O(2-delta) from the corresponding In-doped Ba-containing perovskite of the nominal chemical formula BaCe(1-x)In(x)O(3-delta) at 800 degrees C. The amount of CO(2) gained per ceramic gram was found to be consistent with the formation of BaCO(3), confirming the complete leaching of Ba in BaCe(1-x)In(x)O(3-delta). The CO(2) capture efficiency was found to be in the range of 90-99% at 800 degrees C, which is significantly higher than those of well-known low-temperature CO(2) absorbing materials, including Li(2)O, Li(6)Zr(2)O(7), Li(1.8)Na(0.2)ZrO(3) and LiNaZrO(3). Powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDAX) confirmed the perovskite into fluorite structural transformation reaction. The AC impedance study showed a clear intercept to the real axis at the low-frequency over the investigated temperatures in all the atmospheres, indicating a non-blocking nature of electrode (Pt) and electrolyte interface. The constant phase element (CPE) value was found to be in the order of 10(-10) F in air, N(2) and Ar for high-frequency part of the semicircle due to bulk contribution, and about two orders of magnitude lower values were observed for the low-frequency semicircle which may correspond to grain-boundary effect. The 20 mol% In-doped CeO(2) exhibits a total electrical conductivity of about 4 x 10(-6) S/cm at 600 degrees C in Ar, while in H(2) an about four orders of magnitude higher electrical conductivity of 3 x 10(-2) S/cm was observed. The activation energy for electrical conductivity was found to be 1.36 eV in Ar, 1.43 eV in N(2), 1.34 eV in H(2), and 1.1 eV in air for Ce(0.8)In(0.2)O(1.9).

Revisiting tungsten trioxide hydrates (TTHs) synthesis--is there anything new?

We report a very simple precipitation route to prepare a layered perovskite-type structure, tungsten trioxide hydrate (TTH), with the nominal chemical formula of WO(3) x 1.3 H(2)O (identical with 1/2H(2)W(2)O(7) x 1.6 H(2)O), using aqueous Na(2)WO(4) and SrCl(2). Our investigation shows that the concentration of HCl used to dissolve the SrCl(2) plays a crucial role in the stabilization of different structure types of layered TTHs. Highly acidic SrCl(2) (dissolved in 9 M HCl) solution yields an orthorhombic layered TTH of WO(3) x 2 H(2)O, while SrCl(2) dissolved in 3 M HCl appears to give an A-site-deficient Ruddlesdon-Popper (RP) related double-perovskite-type layered structure (DOLS-TTH). A well-known scheelite-type structure is obtained under weakly basic conditions (pH = 10.3 for Na(2)WO(4(aq)), 7.0 for SrCl(2(aq))). Previously, RP-type a DOLS of H(2)W(2)O(7) x 0.58 H(2)O was prepared, using an acid-leaching method, from the corresponding n = 2 member of the layered Aurivillius phase (AP) Bi(2)W(2)O(9). Powder X-ray diffraction showed the formation of layered RP DOLS with a large d spacing approximately 12.5 A, which is consistent with acid-leaching (Kuto et al. Inorg. Chem. 2003, 42, 4479-4484; Wang et al. J. Solid State Chem. 2007, 180, 1125-1129) and exfoliation (Schaak et al. Chem. Commun. 2002, 706-707) methods for synthesized TTHs. The proposed DOLS-TTH structure of newly prepared TTHs was further confirmed by an intercalation reaction using n-octylamine (C8A). A transmission electron microscopy study showed the formation of nanosized particles, and scanning electron microscopy coupled with energy dispersive X-ray analysis showed the absence of Na and Sr in the air-dried, as-precipitated products under acidic conditions. The bulk electrical (proton) conductivity of presently prepared TTHs was found to be on the order of 10(-4)-10(-3) S/cm at room temperature in wet N(2).

Facile conversion of layered Ruddlesden-Popper-related structure Y2O3-doped Sr2CeO4 into fast oxide ion-conducting fluorite-type Y2O3-doped CeO2.

The present work shows a new solid- and gas-phase reaction technique for the preparation of a fast oxide-ion-conducting Y(2)O(3)-doped Ce(1-x)Y(x)O(2-delta) (x = 0.1, 0.2) (YCO), which involves the reaction of layered (Ruddlesden-Popper K(2)NiF(4)-type) structure Y(2)O(3)-doped Sr(2)CeO(4) (YSCO) with CO(2) at an elevated temperature and subsequent acid-washing. A powder X-ray diffraction study revealed the formation of a single-phase cubic fluorite-type YCO for the CO(2)-reacted and subsequent acid-washed product. Energy dispersive X-ray analysis showed the absence of Sr in the CO(2)-treated and subsequent acid-washed product, confirming the transformation of layered YSCO into YCO. The cubic lattice constant was found to decrease with increasing Y content in YCO, which is consistent with the other YCO samples reported in the literature. The scanning electron microscopy study showed smaller-sized particles for the product obtained after CO(2)- and acid-washed YCO samples, while the high-temperature sintered YCO and the precursor YSCO exhibit larger-sized particles. The bulk ionic conductivity of the present CO(2)-capture-method-prepared YCO exhibits about one and half orders of magnitude higher electrical conductivity than that of the undoped CeO(2) and was found to be comparable to those of ceramic- and wet-chemical-method synthesized rare-earth-doped CeO(2).

Synthesis and cytotoxic activity of some novel polycyclic gamma-butyrolactones.

Baeyer-Villiger oxidation of 5-aryl-7,11,11-trimethyltricyclo[5.4.0.0(3,6)]-undec-1-en-4-ones 4a-h by H(2)O(2) and formic acid in methanol yields mixtures of 3b,7,7-trimethyl-3-phenyl-3,3a,3b,4,5,6,7,8a-octahydro-1H-indeno-[1,2-c]furan-1-ones 8a-h and 3b,7,7-trimethyl-3-phenyl-3,3a,3b,4,5,6,7,8a-octahydro-1H-indeno-[1,2-c]furan-2-ones 9a-h in high yields. The obtained butyrolactones 8a-h display cytotoxic activity against a number of human cancer cells.