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Title: Comparative Study of the Thermal Stabilities of the Experimentally Known High-Valent Fe(IV) Compounds Fe(1-norbornyl) 4 and Fe(cyclohexyl) 4
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Publication Date:
Journal Name:
The Journal of Physical Chemistry A
Page Range or eLocation-ID:
6867 to 6876
Sponsoring Org:
National Science Foundation
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  1. To address critical energy issues in civic structures, we have developed a novel concept of optical thermal insulation (OTI) without relying on a conventional thermal intervention medium, such as air or argon, as often used in conventional window systems. We have synthesized the photothermal (PT) materials, such as the Fe 3 O 4 and Fe 3 O 4 @Cu 2− x S nanoparticles, that exhibit strong UV and near-infrared (NIR) absorptions but with good visible transparency. Upon coating the inner surface of the window glass with a PT film, under solar irradiation, the inner surface temperature rises due to the PT effect. Subsequently, the temperature difference, Δ T , is reduced between the single pane and room interior. This leads to lower the thermal loss through a window, reflected by the U -factor, resulting in considerable energy saving without double- or triple-glazing. Comparing with the Fe 3 O 4 coatings, Fe 3 O 4 @Cu 2− x S is spectrally characterized with a much stronger NIR absorbance, contributing to an increased PT efficiency under simulated solar irradiation (0.1 W/cm 2 ). PT experiments are carried out via both white light and monochromic NIR irradiations (785 nm). The parameters associated withmore »the thermal performance of the PT films are calculated, including PT conversion efficiency, specific absorption rate (SAR), and U -factor. Based on the concept of OTI, we have reached an optimum U -factor of 1.46 W/m 2 K for a single pane, which is satisfactory to the DOE requirement (<1.7 W/m 2 K).« less
  2. Combining experimental and theoretical studies, we investigate the role of R-site (R = Y, Sm, Bi) element on the phase formation and thermal stability of R 2 (Mn 1−x Fe x ) 4 O 10−δ ( x = 0, 0.5, 1) mullite-type oxides. Our results show a distinct R-site dependent phase behavior for mullite-type oxides as Fe is substituted for Mn: 100% mullite-type phase was formed in (Y, Sm, Bi) 2 Mn 4 O 10 ; 55% and 18% of (Y, Sm) 2 Mn 2 Fe 2 O 10−δ was found when R = Y and Sm, respectively, for equal Fe and Mn molar concentrations in the reactants, whereas Bi formed 54% O10- and 42% O9-mixed mullite-type phases. Furthermore, when the reactants contain 100% Fe, no mullite-type phase was formed for R = Y and Sm, but a sub-group transition to Bi 2 Fe 4 O 9 O9-phase was found for R = Bi. Thermogravimetric analysis and density functional theory (DFT) calculation results show a decreasing thermal stability in O10-type structure with increasing Fe incorporation; for example, the decomposition temperature is 1142 K for Bi 2 Mn 2 Fe 2 O 10−δ vs. 1217 K for Bi 2 Mn 4more »O 10 . On the other hand, Bi 2 Fe 4 O 9 O9-type structure is found to be thermally stable up to 1227 K. These findings are explained by electronic structure calculations: (1) as Fe concentration increases, Jahn–Teller distortion results in mid band-gap empty states from unstable Fe 4+ occupied octahedra, which is responsible for the decrease in O10 structure stability; (2) the directional sp orbital hybridization unique to Bi effectively stabilizes the mullite-type structure as Fe replaces Mn.« less