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Creators/Authors contains: "Davis, Ryan"

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  1. Free, publicly-accessible full text available March 6, 2026
  2. The production of ordered mesoporous carbons (OMCs) can be achieved by direct pyrolysis of self-assembled polymers. Typically, these systems require a majority phase capable of producing carbon, and a minority phase to form pores through a thermal decomposition step. While polyacrylonitrile (PAN)-based block copolymers (BCPs) have been broadly reported as OMC precursors, these materials have a relatively narrow processing window for developing ordered nanostructures and often require sophisticated chemistry for BCP synthesis, followed by long crosslinking times at high temperatures. Alternatively, olefinic thermoplastic elastomers (TPEs) can be convered to large-pore OMCs after two steps of sulfonation-induced crosslinking and carbonization. Building on this platform, this work focuses on the precursor design concept for the efficient synthesis of OMCs through employing low-cost and widely available polystyrene-block-polybutadiene-block-polystyrene (SBS), which contains unsaturated bonds along the polymer backbone. As a result, the presence of alkene groups greatly enhances the kinetics of sulfonation-induced crosslinking reaction, which can be completed within only 20 min at 150 °C, nearly an order of magnitude faster than a recently reported TPE system containing a fully saturated polymer backbone. The crosslinking reaction enables the production of OMCs with pore sizes (∼9.5 nm) larger than most conventional soft-templating systems, while also doping sulfur heteroatoms into the carbon framework of the final products. This work demonstrates efficient synthesis of OMCs from TPE precursors which have a great potential for scaled production, and the resulting products may have broad applications such as for drug delivery and energy storage. 
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  3. Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge 1−x Sn x ( x ≈  0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion. 
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  4. Internally-mixed aerosol particles containing organic molecules and inorganic salts are prevalent in the atmosphere, arising from direct emission ( e.g., from the ocean) or indirect production by condensation of organic vapors onto existing inorganic particle seeds. Aerosol particles co-exist with water vapor and, under humid conditions, will exist as dilute aqueous solution particles that can be well described by thermodynamic models. Under low humidity conditions, the increase in solute concentrations leads to molecular interactions and significant non-ideality effects that drive changes in important physical properties, such as viscosity and phase state, that are not predicted using simple models. Here, we explore a model system containing ammonium sulfate (AS) and citric acid (CA). We measure the hygroscopicity, viscosity, and rate of water diffusion in particles across a range of RH conditions and organic fractions to better understand the influence of organic–inorganic mixtures on particle properties. We report the RH dependence of these properties and explore the applicability of commonly used methods that connect them together, such as the Stokes–Einstein relationship and thermodynamic modelling methods. We show that at low RH, the addition of AS to CA leads to a reduction in the amount of water as indicated by the radial growth factor at a fixed RH, while observing an increase in the viscosity over several orders of magnitude. Contrary to the viscosity, only minor changes in water diffusion were measured, and analysis with the fractional Stokes–Einstein relationship indicates that changes in the molecular matrix due to the presence of AS could explain the observed phenomena. This work reveals that small additions of electrolytes can drive large changes in particle properties, with implications for chemical reactivity, lifetime, and particle phase that will influence the environmental impacts and chemistry of aerosol particles. 
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