Iron doped ZnO (Fe-ZnO) nanoparticles were synthesized using two techniques that are economical as well as scalable to yield tunable properties of nanoparticles for facilitating down conversion in an absorbing layer of a solar cell. To evaluate the suitability of Fe-ZnO nanoparticles prepared by two deposition methods, we present a comparison of optical, electrical, and structural properties of Fe-ZnO using several experimental techniques. Structural properties were analyzed using transmission electron microscopy and x-ray diffraction spectroscopy (XRD) with Rietveld analysis for extracting information on compositional variations with Fe doping. The chemical composition of nanoparticles was analyzed through X-ray photoelectron spectroscopy (XPS). The optical properties of nanoparticles were studied using photoluminescence and UV-Vis absorption spectroscopy. In addition, fluorescence lifetime measurement was also performed to study the changes in an exponential decay of lifetimes. The electrical transport properties of Fe-ZnO were analyzed by impedance spectroscopy. Our studies indicate that ethanol as a solvent in a microwave method would produce smaller nanoparticles up to the size of 11 nm. In contrast, the precipitation method produces secondary phases of Fe2O3 beyond 5% doping. In addition, our studies show that the optical and electrical properties of resulting Fe-ZnO nanoparticles depend on the particle sizes and the synthesis techniques used. These new results provide insight into the role of solvents in fabricating Fe-ZnO nanoparticles by precipitation and microwave methods for photovoltaic and other applications.
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Heterometal incorporation in NH 2 -MIL-125(Ti) and its participation in the photoinduced charge-separated excited state
Optical and X-ray spectroscopy studies reveal the location and role of Fe 3+ sites incorporated through direct synthesis in NH 2 -MIL-125(Ti). Fe K-edge XAS analysis confirms its metal–oxo cluster node coordination while time-resolved optical and X-ray transient absorption studies disclose its role as an electron trap site, promoting long-lived photo-induced charge separation in the framework. Notably, XTA measurements show sustained electron reduction of the Fe sites into the microsecond time range. Comparison with an Fe-doped MOF generated through post-synthetic modification indicates that only the direct synthesis approach affords efficient Fe participation in the charge separated excited state.
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- NSF-PAR ID:
- 10206917
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 56
- Issue:
- 78
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 11597 to 11600
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract H2W2O7, a metastable material synthesized via selective etching of the Aurivillius‐related Bi2W2O9, is demonstrated as an electrode for high power proton‐based energy storage. Comprehensive structural characterization is performed to obtain a high‐fidelity crystal structure of H2W2O7using an iterative approach that combines X‐ray diffraction, neutron pair distribution function, scanning transmission electron microscopy, Raman spectroscopy, and density functional theory modeling. Electrochemical characterization shows a capacity retention of ≈80% at 1000 mV s–1(1.5‐s charge/discharge time) as compared to 1 mV s–1(≈16‐min charge/discharge time) with cyclability for over 100 000 cycles. Energetics from density functional theory calculations indicate that proton storage occurs at the terminal oxygen sites within the hydrated interlayer. Last, optical micrographs collected during in situ Raman spectroscopy show reversible, multicolor electrochromism, with color changes from pale yellow to blue, purple, and last, orange as a function of proton content. These results highlight the use of selective etching of layered perovskites for the synthesis of metastable transition metal oxide materials and the use of H2W2O7as an anode material for proton‐based energy storage or electrochromic applications.
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Nanocrystalline MnFe2O4 has shown promise as a catalyst for the oxygen reduction reaction (ORR) in alkaline solutions, but the material has been sparingly studied as highly ordered thin-film catalysts. To examine the role of surface termination and Mn and Fe site occupancy, epitaxial MnFe2O4 and Fe3O4 spinel oxide films were grown on (001)- and (111)-oriented Nb:SrTiO3 perovskite substrates using molecular beam epitaxy and studied as electrocatalysts for the oxygen reduction reaction (ORR). High-resolution X-ray diffraction (HRXRD) and X-ray photoelectron spectroscopy (XPS) show the synthesis of pure phase materials, while scanning transmission electron microscopy (STEM) and reflection high-energy electron diffraction (RHEED) analysis demonstrate island-like growth of (111) surface-terminated pyramids on both (001)- and (111)-oriented substrates, consistent with the literature and attributed to the lattice mismatch between the spinel films and the perovskite substrate. Cyclic voltammograms under a N2 atmosphere revealed distinct redox features for Mn and Fe surface termination based on comparison of MnFe2O4 and Fe3O4. Under an O2 atmosphere, electrocatalytic reduction of oxygen was observed at both Mn and Fe redox features; however, a diffusion-limited current was only achieved at potentials consistent with Fe reduction. This result contrasts with that of nanocrystalline MnFe2O4 reported in the literature where the diffusion-limited current is achieved with Mn-based catalysis. This difference is attributed to a low density of Mn surface termination, as determined by the integration of current from CVs collected under N2, in addition to low conductivity through the MnFe2O4 film due to the degree of inversion. Such low densities are attributed to the synthetic method and island-like growth pattern and highlight challenges in studying ORR catalysis with single-crystal spinel materials.more » « less
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Ferrate(VI) has the potential to play a key role in future water supplies. Its salts have been suggested as “green” alternatives to current advanced oxidation and disinfection methods in water treatment, especially when combined with ultraviolet light to stimulate generation of highly oxidizing Fe(V) and Fe(IV) species. However, the nature of these intermediates, the mechanisms by which they form, and their roles in downstream oxidation reactions remain unclear. Here, we use a combination of optical and X-ray transient absorption spectroscopies to study the formation, interconversion, and relaxation of several excited-state and metastable high-valent iron species following excitation of aqueous potassium ferrate(VI) by ultraviolet and visible light. Branching from the initially populated ligand-to-metal charge transfer state into independent photophysical and photochemical pathways occurs within tens of picoseconds, with the quantum yield for the generation of reactive Fe(V) species determined by relative rates of the competing intersystem crossing and reverse electron transfer processes. Relaxation of the metal-centered states then occurs within 4 ns, while the formation of metastable Fe(V) species occurs in several steps with time constants of 250 ps and 300 ns. Results here improve the mechanistic understanding of the formation and fate of Fe(V) and Fe(IV), which will accelerate the development of novel advanced oxidation processes for water treatment applications.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0CC05339B
