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Nonnenmann, Stephen S.

Publications and source records attributed to Nonnenmann, Stephen S..

7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.

2D nanosheets↗
DOE OSTI2020

Syntrophus conductive pili demonstrate that common hydrogen-donating syntrophs can have a direct electron transfer option

Syntrophic interspecies electron exchange is necessary for the stable functioning of diverse anaerobic microbial communities. Hydrogen/formate interspecies electron transfer (HFIT), in which H 2 and/or formate function as diffusible electron carriers, has been considered to be the primary mechanism for electron transfer because most common syntrophs were thought to lack biochemical components, such as electrically conductive pili (e-pili), necessary for direct interspecies electron transfer (DIET). Herein we report that Syntrophus aciditrophicus, one of the most intensively studied microbial models for HFIT, produces e-pili and can grow via DIET. Heterologous expression of the putative S. aciditrophicus type IV pilin gene in Geobacter sulfurreducens yielded conductive pili of the same diameter (4 nm) and conductance of the native S. aciditrophicus pili and enabled long-range electron transport in G. sulfurreducens. S. aciditrophicus lacked abundant c-type cytochromes often associated with DIET. Pilin genes likely to yield e-pili were found in other genera of hydrogen/formate-producing syntrophs. The discovery that DIET is a likely option for diverse syntrophs that are abundant in many anaerobic environments necessitates a reexamination of the paradigm that HFIT is the predominant mechanism for syntrophic electron exchange within anaerobic microbial communities of biogeochemical and practical significance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Tuning Metastability of Poly(3-hexyl thiophene) Solutions to Enable in Situ Atomic Force Microscopy Imaging of Surface Nucleation

Poly(3-hexyl thiophene) (P3HT), a workhorse material for the study of organic electronic devices, assembles into nanofibers (NFs) upon crystallization from solution, providing the means to tailor morphology and improve device performance. We investigate how P3HT regioregularity, molecular weight, and concentration influence the hysteresis between crystallization and melting temperatures of NFs. Hysteresis is found to increase with molecular weight and reach an asymptote for polymer chains above the chain folding threshold (Mn > 12 kg/mol). Regioregularity does not substantially affect the hysteresis above a level of 88%, while increasing polymer concentration is found to reduce hysteresis. This insight facilitates in situ high-resolution atomic force microscopy measurements that provide better understanding of the mechanism of NF crystallization on graphite. We find an interchain distance (along the a crystallographic axis) of 16.7 ± 0.7 Å, and a spacing of 7.7 ± 0.2 Å along the c axis, suggesting that the crystals on graphite are form I.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Highly Uniform Resistive Switching in HfO 2 Films Embedded with Ordered Metal Nanoisland Arrays

Memristors enter a critical developmental stage where emerging large-scale integration methods face major challenges with severe switching instabilities in the oxide layer. In this work, the superior uniformity is achieved within HfO 2 films by embedding highly ordered metal nanoisland (NI) arrays. Embedded films exhibit a significant reduction in both SET and RESET while displaying enhanced uniformity in operating voltages and resistance states. This behavior is attributed to the concentration of electric fields along Pt and Ti NIs and their interactions with the surrounding oxide film matrix environment, which induce separate and distinct filamentary formation mechanisms that affect the stability. A method is reported to further optimize the uniformity of the SET voltage by translating the NI array position down the film-thickness dimension towards the bottom electrode. A comparison of the density and distribution of the oxygen vacancies responsible for the formation/dissolution of conducting filaments is made via combined electrostatic force microscopy and conductive atomic force microscopy (c-AFM) studies. Finally, complete observation of the morphological evolution of conducting filaments produced by Pt and Ti is enabled by 3D c-AFM nanotomography and cross-sectional scanning transmission electron microscopy–energy dispersive spectroscopy to provide direct correlations between NI-oxide interactions and overall switching performance.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Probing vacancy behavior across complex oxide heterointerfaces

Oxygen vacancies ( V O ● ● ) play a critical role as defects in complex oxides in establishing functionality in systems including memristors, all-oxide electronics, and electrochemical cells that comprise metal-insulator-metal or complex oxide heterostructure configurations. Improving oxide-oxide interfaces necessitates a direct, spatial understanding of vacancy distributions that define electrochemically active regions. We show vacancies deplete over micrometer-level distances in Nb-doped SrTiO 3 (Nb:SrTiO 3 ) substrates due to deposition and post-annealing processes. We convert the surface potential across a strontium titanate/yttria-stabilized zirconia (STO/YSZ) heterostructured film to spatial (<100 nm) vacancy profiles within STO using ( T = 500°C) in situ scanning probes and semiconductor analysis. Oxygen scavenging occurring during pulsed laser deposition reduces Nb:STO substantially, which partially reoxidizes in an oxygen-rich environment upon cooling. These results (i) introduce the means to spatially resolve quantitative vacancy distributions across oxide films and (ii) indicate the mechanisms by which oxide thin films enhance and then deplete vacancies within the underlying substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Perovskite nickelates as electric-field sensors in salt water

Designing materials to function in harsh environments, such as conductive aqueous media, is a problem of broad interest to a range of technologies, including energy, ocean monitoring and biological applications. The main challenge is to retain the stability and morphology of the material as it interacts dynamically with the surrounding environment. Materials that respond to mild stimuli through collective phase transitions and amplify signals could open up new avenues for sensing. Here we present the discovery of an electric-field-driven, water-mediated reversible phase change in a perovskite-structured nickelate, SmNiO 3 . This prototypical strongly correlated quantum material is stable in salt water, does not corrode, and allows exchange of protons with the surrounding water at ambient temperature, with the concurrent modification in electrical resistance and optical properties being capable of multi-modal readout. Besides operating both as thermistors and pH sensors, devices made of this material can detect sub-volt electric potentials in salt water. Finally, we postulate that such devices could be used in oceanic environments for monitoring electrical signals from various maritime vessels and sea creatures

36 MATERIALS SCIENCE↗