- Award ID(s):
- NSF-PAR ID:
- Date Published:
- Journal Name:
- MRS Communications
- Page Range / eLocation ID:
- 155 to 163
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)The photothermal experiments on the incident light angle dependence are carried out using simulated solar light on thin films of both iron oxides (Fe3O4 and Fe3O4@Cu2-xS) and porphyrin compounds (chlorophyll and chlorophyllin). Fe3O4 and Fe3O4@Cu2-xS are synthesized using various solution methods that produce mono-dispersed nanoparticles on the order of 10 nm. Chlorophyll is extracted from fresh spinach and chlorophyllin sodium copper is a commercial product. These photothermal (PT) materials are dispersed in polymethyl methacrylate (PMMA) solutions and deposited on glass substrates via spin coating that result in clear and transparent thin films. The iron-oxide based thin films show distinctive absorption spectra; Fe3O4 exhibits a strong peak near UV and gradually decreases into the visible and NIR regions; the absorption of Fe3O4@Cu2-xS is similar in the UV region but shows a broad absorption in the NIR region. Both chlorophyll and chlorophyllin are characterized with absorption peaks near UV and NIR showing a “U”-shaped spectrum, ideally required for efficient solar harvest and high transparency in energy-efficient single-pane window applications. Upon coating of the transparent PT films on the window inner surfaces, solar irradiation induces the photothermal effect, consequently raising the film temperature. In this fashion, the thermal loss through the window can be significantly lowered by reducing the temperature difference between the window inner surface and the room interior, based on a new concept of so-called “optical thermal insulation” (OTI) without any intervention medium, such as air/argon, as required in the glazing technologies. Single-panes are therefore possible to replace double- or triple panes. As OTI is inevitably affected by seasonal and daily sunlight changes, an incident light angle dependence of the photothermal effect is crucial in both thin film and window designs. It is found that the heating curves reach their maxima at small angles of incidence while the photothermal effect is considerably reduced at large angles. This angle dependence is well explained by light reflection by the thin film surface, however, deviated from what is predicted by the Fresnel’s law, attributable to non-ideal surfaces of the substrates. The angle dependence data provides an important reference for OTI that window exposure to sun is greater at winter solstice while that is considerably reduced in the summer. This conclusion indicates much enhanced solar harvesting and heat conversion via optically insulated windows in the winter season, resulting in much lower U-factors.more » « less
Long duration energy storage (LDES) is economically attractive to accelerate widespread renewable energy deployment. But none of the existing energy storage technologies can meet LDES cost requirements. The newly emerged solid oxide iron air battery (SOIAB) with energy-dense solid Fe as an energy storage material is a competitive LDES-suitable technology compared to conventional counterparts. However, the performance of SOIAB is critically limited by the kinetics of Fe3O4reduction (equivalent to charging process) and the understanding of this kinetic bottleneck is significantly lacking in the literature. Here, we report a systematic kinetic study of Fe3O4-to-Fe reduction in H2/H2O environment, particularly the effect of catalyst (iridium) and supporting oxides (ZrO2and BaZr0.4Ce0.4Y0.1Yb0.1O3). With in situ created Fe3O4, the degree of reduction is measured by the change of H2O and H2concentrations in the effluent using a mass spectrometer, from which the kinetic rate constant is extracted as a function of inlet H2concentration and temperature. We find that kinetics can be nicely described by Johson-Mehl-Avrami (JMA) model. We also discuss the stepwise reduction mechanisms and activation energy for the reduction process.
This work elucidates the structural evolution of a commercial‐type iron oxide‐based high temperature water–gas shift (HT‐WGS) catalyst during activation and deactivation stages. The findings highlight the importance of Cu–FeO
xinterfaces. Based on the new insights, future improvement of commercial iron‐based catalysts should focus on stabilization of the active Cu–FeO xinterface. Much effort has been devoted to understanding the structure, mechanism, and promotion of the commercial‐type CuO–Cr2O3–Fe2O3catalyst for the high temperature water–gas shift (HT‐WGS) reaction. However, structural evolution of the catalyst during the activation and deactivation stages was rarely reported. Herein, catalyst characterization, temperature‐programmed studies, and kinetic analysis were conducted on iron oxide‐based HT‐WGS catalysts. Addition of Cu was found to accelerate both the bulk (Fe2O3 → Fe3O4) and surface (active FeO x–Cu interface) transformations during the catalyst activation stage. During catalyst deactivation, Cu accelerated both sintering of the Fe3O4bulk phase and unfavorable encapsulation of the metallic Cu particles with a substantial FeO xoverlayer. The loss of the initial active Cu–FeO xinterfacial sites reversed the promotional effect of Cu.
Bacterial cellulose nanocrystals (BCNCs) are biocompatible cellulose nanomaterials that can host guest nanoparticles to form hybrid nanocomposites with a wide range of applications. Herein, we report the synthesis of a hybrid nanocomposite that consists of plasmonic gold nanoparticles (AuNPs) and superparamagnetic iron oxide (Fe 3 O 4 ) nanoparticles supported on BCNCs. As a proof of concept, the hybrid nanocomposites were employed to isolate and detect malachite green isothiocyanate (MGITC) via magnetic separation and surface-enhanced Raman scattering (SERS). Different initial gold precursor (Au 3+ ) concentrations altered the size and morphology of the AuNPs formed on the nanocomposites. The use of 5 and 10 mM Au 3+ led to a heterogenous mix of spherical and nanoplate AuNPs with increased SERS enhancements, as compared to the more uniform AuNPs formed using 1 mM Au 3+ . Rapid and sensitive detection of MGITC at concentrations as low as 10 −10 M was achieved. The SERS intensity of the normalized Raman peak at 1175 cm −1 exhibited a log-linear relationship for MGITC concentrations between 2 × 10 −10 and 2 × 10 −5 M for Au@Fe 3 O 4 @BCNCs. These results suggest the potential of these hybrid nanocomposites for application in a broad range of analyte detection strategies.more » « less
Super‐Earths ranging up to 10 Earth masses (ME) with Earth‐like density are common among the observed exoplanets thus far, but their measured masses and radii do not uniquely elucidate their internal structure. Exploring the phase transitions in the Mg‐silicates that define the mantle‐structure of super‐Earths is critical to characterizing their interiors, yet the relevant terapascal conditions are experimentally challenging for direct structural analysis. Here we investigated the crystal chemistry of Fe3O4as a low‐pressure analog to Mg2SiO4between 45–115 GPa and up to 3000 K using powder and single crystal X‐ray diffraction in the laser‐heated diamond anvil cell. Between 60–115 GPa and above 2000 K, Fe3O4adopts an 8‐fold coordinated Th3P4‐type structure (
I‐43d, Z= 4) with disordered Fe2+and Fe3+into one metal site. This Fe‐oxide phase is isostructural with that predicted for Mg2SiO4above 500 GPa in super‐Earth mantles and suggests that Mg2SiO4can incorporate both ferric and ferrous iron at these conditions. The pressure‐volume behavior observed in this 8‐fold coordinated Fe3O4indicates a maximum 4% density increase across the 6‐ to 8‐fold coordination transition in the analog Mg‐silicate. Reassessment of the FeO—Fe3O4fugacity buffer considering the Fe3O4phase relationships identified in this study reveals that increasing pressure and temperature to 120 GPa and 3000 K in Earth and planetary mantles drives iron toward oxidation.