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Ryan, Bradley J.

Publications and source records attributed to Ryan, Bradley J..

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Melt-Processed Halide Perovskite Thin Films from a Two-Dimensional Ruddlesden–Popper Phase Precursor

While halide perovskite thin films have enormous potential for photovoltaics and other optoelectronics, the use of environmentally hazardous solvents during their deposition and processing poses a barrier to their commercialization. In this work, we demonstrated the deposition of melt-processable precursors and subsequent transformation into halide perovskite thin films without using environmentally hazardous solvents. We melted the wide-bandgap layered perovskites [(C 6 H 5 CH(CH 3 )CH 2 NH 3 ) 2 PbI 4 :β-Me-PEA 2 PbI 4 ] at ~210 °C and blade coated them into films. The β-Me-PEA 2 PbI 4 films were subsequently transformed to perovskite-phase methylammonium or formamidinium lead iodide films using a cation-exchange process in an alcohol-based solvent. Lastly, we demonstrate the potential and limitations of a completely solvent-free approach that uses solid-state transformation of a β-Me-PEA 2 PbI 4 film. As a result, this work represents a substantial step toward eliminating environmentally hazardous solvents and enables inexpensive industrial-scale liquid-phase deposition processes that do not require expensive systems for handling and disposing of environmentally hazardous solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Chlorination of Hydrogenated Silicon Nanosheets Revealed by Solid-State Nuclear Magnetic Resonance Spectroscopy

We report two-dimensional silicon nanosheets (Si-NS) synthesized by topotactic deintercalation of CaSi 2 are hypothesized to consist of buckled layers of sp 3 -hybridized silicon atoms that are bonded to three other framework Si atoms and a terminal atom or functional group such as H, Cl, or OH. Here, we apply 1 H{ 35 Cl} and 29 Si{ 35 Cl} Resonance-Echo Saturation-Pulse DOuble-Resonance (RESPDOR) solid-state NMR experiments to directly confirm the presence of chlorinated Si atoms within Si-NS. Plotting the 1 H{ 35 Cl} RESPDOR dephasing as a function of the 35 Cl saturation pulse offset reveals that the 35 Cl quadrupolar coupling constant (C Q ) is 38 MHz, consistent with Cl atoms that are covalently bonded to silicon. Modeling the 1 H{ 35 Cl} RESPDOR dephasing curve shows that the Si–Si interlayer spacing is approximately 6 Å. Plane-wave density functional theory (DFT) calculations show that the direct band gap transition of the Si-NS decreases with increasing chlorination and hydroxylation, suggesting that the band gap of Si-NS can be tuned by modifying the terminal atoms or functional groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Triacetic Acid Lactone and 4-Hydroxycoumarin as Bioprivileged Molecules for the Development of Performance-Advantaged Organic Corrosion Inhibitors

Biomass conversion, especially the development of bioprivileged molecules utilizing integration of biological and chemical processes, has shown potential to produce novel chemicals with enhanced properties. Here, organic corrosion inhibitors based on triacetic acid lactone and 4-hydroxycoumarin have been synthesized in good yield and tested for corrosion inhibition on mild steel in both sulfuric acid and hydrochloric acid. Sixteen novel corrosion inhibitors derived from triacetic acid lactone and 4-hydroxycoumarin were efficiently synthesized and twelve of them showed high corrosion inhibition efficiency as confirmed by electrochemical impedance spectroscopy (giving values greater than 78%) and polarization analysis. While triacetic acid lactone-based compounds showed good corrosion inhibition performance, the 4-hydroxycoumarin-based compounds showed further improvement in corrosion inhibition performance. Scanning electron microscopy (SEM) analysis of the mild steel coupon in the presence of selected inhibitors showed that corrosion was significantly diminished, with complementary X-ray photoelectron spectroscopy (XPS) analysis suggesting the inhibitor molecules strongly adsorbed on the steel surface. Quantum chemical calculations showed poor correlation between calculated parameters and the performance of these molecules. This large set of corrosion inhibitors containing a dozen promising corrosion inhibitors is useful for future rational design of corrosion inhibitors. In conclusion, the results demonstrate a new direction for the development of bioprivileged molecules.

09 BIOMASS FUELS↗
DOE OSTI2021

Local Structural Disorder in Metavanadates MV 2 O 6 (M = Zn and Cu) Synthesized by the Deep Eutectic Solvent Route: Photoactive Oxides with Oxygen Vacancies

Metavanadates MV 2 O 6–δ (M = Zn and Cu) are synthesized by using a deep eutectic solvent (DES), a mixture of hydrogen bond donor and acceptor, as a reaction medium. Dissolution of stable binary metal oxides in a DES followed by a heat treatment yields phase-pure vanadates. According to in situ powder X-ray diffraction, ternary phases (α-Zn 2 V 2 O 7 and β-Cu 2–x V 2 O 7 , x ~ 0.27) are intermediates in the reaction pathway taken. Identifying a polymorphic phase transformation temperature for CuV 2 O 6 as well as the narrow temperature range between formation and decomposition for both metavanadates allows for tackling the challenge of the synthesis of these materials. The oxygen vacancy introduced by the DES route is accompanied by the formation of reduced V 4+ and Cu + in the oxide matrix, based on X-ray photoelectron spectroscopy. These oxygen vacancies modify the vibrational modes in the corresponding Raman spectra and are also responsible for broad optical absorptions in the 1.8–1.1 eV range. The optical band gaps of the materials are found at 1.8 eV (CuV 2 O 6 ) and 2.2 eV (ZnV 2 O 6 ), approximately 0.1–0.3 eV below the values reported in the literature. The reduced band gaps and sub-band gap photon absorption are key features of the oxygen-deficient metavanadates. Surface photovoltage spectroscopy reveals that all the synthesized vanadates are n-type materials with electrons as the majority charge carriers, and photoelectrochemical measurements confirm photoanodic currents for methanol oxidation. Furthermore, these results provide insight into the synthesis and structure–property relationship of the metavanadates for their potential use as photoanodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗