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The apparent PTCR effect in layered alkali titanates - A correlation between temperature dependent electrical properties and thermal analyses
(2024-12-01)
Pulphol, Phieraya
;
Chaithaweep, Kanokwan
;
Vittayakorn, Naratip
;
Maluangnont, Tosapol
Adsorbed water promotes proton conduction in ceramics at ambient conditions prior to its evaporation, apparently leading to the positive temperature coefficient of resistivity (PTCR) effect. Using surface water-containing Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> (1.8 mol water/mol titanate) as an example, the static conductivity (at 50 °C) of ∼10−5 S cm−1 is one thousand times that at 200 °C due to the enhanced proton conduction. At 50–150 °C, the conductivity decreases by 4 orders of magnitude because water evaporation decreases the number of charge carriers. At 150–400 °C, the conduction in water-free Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> is thermal-activated with the apparent activation energy E<inf>a</inf> ∼58–72 kJ mol−1, depending on the formalisms. We show clearly that an endothermic DSC peak (water evaporation) in Cs<inf>2</inf>Ti<inf>6</inf>O<inf>13</inf> coincides with all eight presentations of AC properties examined. Similar correlations are obtained from the TG/DTG curves in Cs<inf>2</inf>Ti<inf>5</inf>O<inf>11</inf>·H<inf>2</inf>O containing mostly intercalated water. The correlation between thermal analyses and AC properties points out that water molecules essentially contribute to the charge transport at ambient conditions of layered alkali titanates. This scenario might be potentially extended to other humidity-sensitive ceramics.
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Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid
(2016-06-01)
Maluangnont, Tosapol
;
Arsa, Pornanan
;
Limsakul, Kanokporn
;
Juntarachairot, Songsit
;
Sangsan, Saithong
While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K<inf>0.8</inf>Zn<inf>0.4</inf>Ti<inf>1.6</inf>O<inf>4</inf> as an example. The low basicity (0.04 mmol CO<inf>2</inf>/g) and low desorption temperature (50-300 °C) shown by CO<inf>2</inf>- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO<inf>2</inf>. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C<inf>16</inf> acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C<inf>31</inf> ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

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