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Abstract The formation of compressible porous sponge electrodes is appealing to overcome diffusion limitations in porous electrodes for applications including electrochemical energy storage, electrochemical water desalination, and electrocatalysis. Previous work has employed wet chemical synthesis to deliver conductive materials into porous polymer sponge supports, but these approaches struggle to produce functional electrodes due to (1) poor electrical connectivity of the conductive network and (2) mechanical rigidity of the foam after coating. In this work we employ oxidative molecular layer deposition (oMLD) via sequential gas-phase exposures of 3,4 ethylenedioxythiophene (EDOT) and molybdenum pentachloride (MoCl 5 ) oxidant to imbibe polyurethane sponges with electrically-conductive and redox-active poly(3,4 ethylenedioxythiophene) (PEDOT) coatings. We analyze the oMLD deposition on compressive polyurethane sponges and modify the reaction conditions to obtain mechanically compressible and electrically conductive sponge electrodes. We specifically identify the importance MoCl5 dose time to enhance the conductivity of the sponges and the importance of EDOT purge time to preserve the mechanical properties of the sponges. Controlling these variables produces an electrically conductive PEDOT network within the sponge support with reduced impact on the sponge’s mechanical properties, offering advantages over wet-chemical synthesis approaches. The compressible, conductive sponges we generate have the potential to be used as compressible electrodes for water desalination, energy storage, and electrocatalysis.   

Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly attractive for these applications to enable faster charging. Recent work has demonstrated that nanoscale thin films of PEDOT can be formed using sequential gas-phase exposures via oxidative molecular layer deposition, or oMLD, which provides advantages in conformality and uniformity on high aspect ratio substrates over other deposition techniques. But to date, the electrochemical properties of these oMLD PEDOT thin films have not been well-characterized. In this work, we examine the electrochemical properties of 5–100 nm thick PEDOT films formed using 20–175 oMLD deposition cycles. We find that film thickness of oMLD PEDOT films affects the orientation of ordered domains leading to a substantial change in charge storage capacity. Interestingly, we observe a minimum in charge storage capacity for an oMLD PEDOT film thickness of ∼30 nm (60 oMLD cycles at 150 °C), coinciding with the highest degree of face-on oriented PEDOT domains as measured using grazing incidence wide angle X-ray scattering (GIWAXS). Thinner and thicker oMLD PEDOT films exhibit higher fractions of oblique (off-angle) orientations and corresponding increases in charge capacity of up to 120 mA h g −1 . Electrochemical measurements suggest that higher charge capacity in films with mixed domain orientation arise from the facile transport of ions from the liquid electrolyte into the PEDOT layer. Greater exposure of the electrolyte to PEDOT domain edges is posited to facilitate faster ion transport in these mixed domain films. These insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment. 

Direct laser scribing of molybdenum dioxide is enabled on soft elastomers to build Janus wearables and reshapable devices. 

We report on a multi‐method sourcing study of 35 mineral pigment artefacts from the Middle Stone Age site of Pinnacle Point 5–6 North (PP5–6 N), dating from about 90–50 ka. The artefacts were analysed and compared with geological samples from seven sources using neutron activation analysis (NAA), and supplemented by data from X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Our preliminary results suggest that the occupants of PP5–6 N likely used at least two local and one currently unidentified and possibly non‐local Fe oxide mineral pigment sources. The mineral pigment artefacts derived from the latter source(s) exhibited manganese (Mn) enrichment with concentrations well above those observed in all sampled source deposits in the study area, suggesting a distinctive formation process. The proportions of the Mn‐enriched mineral pigment artefacts within the PP5–6 N assemblage vary over time, but tend to occur at higher rates in the glacial Marine Isotope Stage (MIS) 4 deposits, which holds potential implications for changes in the use of sources over time, increased mobility or increased exchange during this period.

 

Investigations in the now-submerged cave systems on the Yucatán Peninsula continue to yield evidence for human presence during the Pleistocene-Holocene transition. Skeletal remains are scattered throughout the caves of Quintana Roo, most representing individuals who died in situ. The reasons why they explored these underground environments have remained unclear. Here, we announce the discovery of the first subterranean ochre mine of Paleoindian age found in the Americas, offering compelling evidence for mining in three cave systems on the eastern Yucatán over a ~2000-year period between ~12 and 10 ka. The cave passages exhibit preserved evidence for ochre extraction pits, speleothem digging tools, shattered and piled flowstone debris, cairn navigational markers, and hearths yielding charcoal from highly resinous wood species. The sophistication and extent of the activities demonstrate a readiness to venture into the dark zones of the caves to prospect and collect what was evidently a highly valued mineral resource. 

Red mineral pigment use is recognized as a fundamental component of a series of traits associated with human evolutionary development, social interaction, and behavioral complexity. Iron-enriched mineral deposits have been collected and prepared as pigment for use in rock art, personal adornment, and mortuary practices for millennia, yet little is known about early developments in mineral processing techniques in North America. Microanalysis of rock art pigments from the North American Pacific Northwest reveals a sophisticated use of iron oxide produced by the biomineralizing bacteriumLeptothrix ochracea;a keystone species of chemolithotroph recognized in recent advances in the development of thermostable, colorfast biomaterial pigments. Here we show evidence for human engagement with this bacterium, including nanostructural and magnetic properties evident of thermal enhancement, indicating that controlled use of pyrotechnology was a key feature of how biogenic iron oxides were prepared into paint. Our results demonstrate that hunter-gatherers in this area of study prepared pigments by harvesting aquatic microbial iron mats dominated by iron-oxidizing bacteria, which were subsequently heated in large open hearths at a controlled range of 750 °C to 850 °C. This technical gesture was performed to enhance color properties, and increase colorfastness and resistance to degradation. This skilled production of highly thermostable and long-lasting rock art paint represents a specialized technological innovation. Our results contribute to a growing body of knowledge on historical-ecological resource use practices in the Pacific Northwest during the Late Holocene.

Figshare link to figures:https://figshare.com/s/9392a0081632c20e9484.