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At least 127 records · Page 7

Integrating the Fields of Catalysis: Active Site Engineering in Metal Cluster, Metal Organic Framework and Metal Single Site

Research evolved using nanoparticles synthesized and characterized under reaction conditions opened the door to study all three fields of catalysis: heterogeneous, homogenous, and enzyme. Fundamental studies of catalytic reactions ranging from hydrogenation to understand Fischer-Tropsch synthesis and isomerization ultimately led to the integration of three fields of catalysis. Our recent work on bridging heterogeneous, homogenous, and enzymatic catalysis was present including functionalization of dendrimer encapsulated metal clusters surface for lactonization, active site engineering in metal organic framework catalysts for methanol production and oligomerization, and single site catalyst for hydrogen production. We envision that the combination of active site engineering and unifying fields of catalysis could be applied to solve practical issues of science-based technology and develop new fields useful in energy research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pyromellitic diimide based bipolar molecule for total organic symmetric redox flow battery

Non-aqueous redox flow batteries based on total organic electrolytes, consisting of earth-abundant elements, i.e., C, H, N, O, are regarded as a promising technology for sustainable and large-scale energy storage. In particular, bipolar redox-active organic materials (BROMs) are distinctly fascinating as electroactive species because they have multiple oxidation states and can undergo multiple redox processes. By virtue of this unique characteristic, BROMs can be utilized as both anolyte and catholyte in symmetric flow batteries, consequently, helping alleviate cross-contamination issues. Here, in this paper, we report an all-organic symmetric redox flow battery based on diimide molecule as a bipolar electroactive material. The potential interval between the cathodic peak and the inner and outer anodic peaks led to a promising cell voltage of 2.22 V. The symmetric battery can be operated at a current density of 20 mA cm -2 , with a coulombic efficiency of 90% for over 100 cycles. This work proposes an alternative approach to designing multi-electron organic redox active materials to facilitate the advancement of high-density symmetric flow batteries.

25 ENERGY STORAGE↗

Metal–Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation

The local environment of a metal active site plays an important role in affecting catalytic activity and selectivity. In re-cent studies, tailoring the behavior of a molybdenum-based active site via modulation of the first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise from these modifications is nontrivial, especially in heterogeneous systems. To this end, the tunability of metal–organic frameworks (MOFs) makes them promising scaffolds for controlling the coordination sphere of a heterogene-ous, catalytically-active metal site while offering additional, attractive features such as crystallinity and high porosity. Herein, we report a variety of MOF-supported Mo species, which were investigated for catalytic thioanisole oxidation to methyl phenyl sulfoxide and/or methyl phenyl sulfone using tert-butyl hydroperoxide (tBHP) as the oxidant. In particular, MOFs of contrasting node architectures were targeted, presenting a unique opportunity to investigate ste-reoelectronic control of Mo active sites in a systematic manner. A Zr 6 -based MOF, NU-1000, was employed along with its sulfated analog Zr 6 -based NU-1000-SO 4 to anchor a dioxymolybdenum species, which enabled examination of sup-port-mediated active site polarizability on catalytic performance. In addition, a MOF containing a mixed metal node, Mo-MFU-4l, was used to probe the stereoelectronic impact of an N-donor ligand environment on the catalytic activity of the transmetalated Mo center. Furthermore, characterization techniques including single crystal X-ray diffraction, were concomi-tantly used with reaction kinetic profiles to better comprehend the dynamics of different Mo active sites, thus correlat-ing structural change with activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The development and applications of multidimensional biomolecular spectroscopy illustrated by photosynthetic light harvesting

The parallel and synergistic developments of atomic resolution structural information, new spectroscopic methods, their underpinning formalism, and the application of sophisticated theoretical methods have led to a step function change in our understanding of photosynthetic light harvesting, the process by which photosynthetic organisms collect solar energy and supply it to their reaction centers to initiate the chemistry of photosynthesis. The new spectroscopic methods, in particular multidimensional spectroscopies, have enabled a transition from recording rates of processes to focusing on mechanism. We discuss two ultrafast spectroscopies – two-dimensional electronic spectroscopy and two-dimensional electronic-vibrational spectroscopy – and illustrate their development through the lens of photosynthetic light harvesting. Both spectroscopies provide enhanced spectral resolution and, in different ways, reveal pathways of energy flow and coherent oscillations which relate to the quantum mechanical mixing of, for example, electronic excitations (excitons) and nuclear motions. The new types of information present in these spectra provoked the application of sophisticated quantum dynamical theories to describe the temporal evolution of the spectra and provide new questions for experimental investigation. While multidimensional spectroscopies have applications in many other areas of science, we feel that the investigation of photosynthetic light harvesting has had the largest influence on the development of spectroscopic and theoretical methods for the study of quantum dynamics in biology, hence the focus of this review. We conclude with key questions for the next decade of this review.

59 BASIC BIOLOGICAL SCIENCES↗

Platform for efficient large-scale storage and analysis of multi-omics data in plant and microbial systems (Final Technical Report)

Genomic variation at the sequence level fundamentally affects the phenotypic state of all organisms at all stages of development, while dynamic processes such as changes in the epigenome (e.g. DNA methylation state) and transcriptome regulate the specific phenotype expressed at any given state of development based upon that genomic variation. In plants, DNA methylation is a particularly important mechanism for both regulating transcriptomic expression and for management of genomic variations that could be deleterious to the organism due to the presence of active retrotransposons in plant genomes. While DNA methylation is heritable, it is also dynamic through a given plant’s development and life cycle, particularly during the development from seed to mature specimen suggesting variations in DNA methylation could be critical regulators of biologically and commercially important phenotypes such as time to flowering; in addition, plant DNA methylation is more complex than that of animals, with methylation of CHG and CHH trinucleotides evident in addition to the better-known CG methylation. The complexity of plant DNA methylation and its interplay with genomic sequence variation, transcriptomics and other epigenomic factors demand a storage and analysis framework that can cope with the complexity both within a single specimen and with analyses that span many individuals and even many species, such as attempts to extend models from model organisms to commercially relevant species. In addition to complexity, the rapid development and proliferation of sequencing technology has led to an explosion of data volume that conventional storage and analysis solutions will likely be unable to cope with in the long run. We proposed to study these with suitable distributed storage and computation and therefore for the application of cloud computing to biological analyses; integrate with existing data sources and compatible with virtually any interface use case, from fully automated shell scripts to notebooks and do all these at scale in this STTR grant.

60 APPLIED LIFE SCIENCES↗

Determining the biogeochemical transformations of organic matter composition in rivers using molecular signatures

Inland waters are hotspots for biogeochemical activity, but the environmental and biological factors that govern the transformation of organic matter (OM) flowing through them are still poorly constrained. Here we evaluate data from a crowdsourced sampling campaign led by the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium to investigate broad continental-scale trends in OM composition compared to localized events that influence biogeochemical transformations. Samples from two different OM compartments, sediments and surface water, were collected from 97 streams throughout the Northern Hemisphere and analyzed to identify differences in biogeochemical processes involved in OM transformations. By using dimensional reduction techniques, we identified that putative biogeochemical transformations and microbial respiration rates vary across sediment and surface water along river continua independent of latitude (18°N–68°N). In contrast, we reveal small- and large-scale patterns in OM composition related to local (sediment vs. water column) and reach (stream order, latitude) characteristics. These patterns lay the foundation to modeling the linkage between ecological processes and biogeochemical signals. We further showed how spatial, physical, and biogeochemical factors influence the reactivity of the two OM pools in local reaches yet find emergent broad-scale patterns between OM concentrations and stream order. OM processing will likely change as hydrologic flow regimes shift and vertical mixing occurs on different spatial and temporal scales. As our planet continues to warm and the timing and magnitude of surface and subsurface flows shift, understanding changes in OM cycling across hydrologic systems is critical, given the unknown broad-scale responses and consequences for riverine OM.

rivers↗

Anatomy of an agricultural antagonist: Feeding complex structure and function of three xylem sap‐feeding insects illuminated with synchrotron‐based 3D imaging

Abstract Many insects feed on xylem or phloem sap of vascular plants. Although physical damage to the plant is minimal, the process of insect feeding can transmit lethal viruses and bacterial pathogens. Disparities between insect‐mediated pathogen transmission efficiency have been identified among xylem sap‐feeding insects; however, the mechanistic drivers of these trends are unclear. Identifying and understanding the structural factors and associated integrated functional components that may ultimately determine these disparities are critical for managing plant diseases. Here, we applied synchrotron‐based X‐ray microcomputed tomography to digitally reconstruct the morphology of three xylem sap‐feeding insect vectors of plant pathogens: Graphocephala atropunctata (blue‐green sharpshooter; Hemiptera, Cicadellidae) and Homalodisca vitripennis (glassy‐winged sharpshooter; Hemiptera, Cicadellidae), and the spittlebug Philaenus spumarius (meadow spittlebug; Hemiptera, Aphrophoridae). The application of this technique revealed previously undescribed anatomical features of these organisms, such as key components of the salivary complex. The visualization of the 3D structure of the precibarial valve led to new insights into the mechanism of how this structure functions. Morphological disparities with functional implications between taxa were highlighted as well, including the morphology and volume of the cibarial dilator musculature responsible for extracting xylem sap, which has implications for force application capabilities. These morphological insights will be used to target analyses illuminating functional differences in feeding behavior.

3D imaging↗

The impact of freeze-thaw history on soil carbon response to experimental freeze-thaw cycles

This dataset contains data used for the paper "The impact of freeze-thaw history on soil carbon response to experimental freeze-thaw cycles". The Related References field will be updated with a full citation when available.Freeze-thaw is a disturbance process in cold regions where permafrost soils are becoming vulnerable to temperature fluctuations above 0˚C. Freeze-thaw alters soil physical and biogeochemical properties with implications for carbon persistence and emissions in Arctic landscapes. We examined whether different freeze-thaw histories in two soil systems led to contrasting biogeochemical responses under a laboratory-controlled freeze-thaw incubation. We investigated controls on soil organic matter (SOM) composition through Fourier-transform ion cyclotron resonance mass spectroscopy (FT-ICR-MS) to identify nominal carbon oxidation states and relative abundances of aliphatic-type carbon molecules in both surface and subsurface soils. Soil cores (~ 60 cm-depth) were sampled from two sites in Alaskan permafrost landscapes with different in situ freeze-thaw characteristics: Healy (>40 freeze-thaw cycles annually) and Toolik (<150 freeze-thaw cycles annually). FT-ICR-MS was coupled with in situ temperature data and soil properties (i.e., soil texture, mineralogy) to assess (1) differences in SOM composition associated with previous freeze-thaw history and (2) sensitivity to experimental freeze-thaw in the extracted cores. Control (freeze-only) samples showed greater carbon oxidation in Healy soils compared with Toolik, even in lower mineral horizons where freeze-thaw history was comparable across both sites. Healy showed the most loss of carbon compounds following experimental freeze-thaw in the lower mineral depths, including a decrease in aliphatics. Toolik soils responded more slowly to freeze-thaw as shown by intermediary carbon oxidation distributed across multiple carbon compound classes. Variations in the response of permafrost carbon chemistry to freeze-thaw is an important factor for predicting changes in soil function as permafrost thaws in high northern latitudes.This dataset contains a compressed (.zip) archive of the data and R scripts used for this manuscript. The dataset includes files in .csv format, which can be accessed and processed using MS Excel or R. This archive can also be accessed on GitHub at https://github.com/Erin-Rooney/FTC-FTICR (DOI 10.5281/zenodo.6533064).

54 ENVIRONMENTAL SCIENCES↗

CdTe Core: Final Technical Report (FTR)

CdTe is presently the cost-leading thin-film PV technology, directly competing with Si at scale, even when domestically manufactured. While an impressive technology, its efficiency remains much below the detailed balance limit with the largest cause due to its low photovoltage and fill factor. To realize gains, the carrier concentration, minority carrier lifetime, and interface recombination all need to be improved simultaneously over historic levels. Using a new defect chemistry (group V doping instead of copper) has been identified as a viable route using single crystal systems. This project focused on implementing this new defect chemistry in scalable, polycrystalline thin-film photovoltaic CdTe devices with tasks focusing improvements to the front interface, absorber, and rear interface as well as capability development & stakeholder engagement. The goal of the project was to establish a strategy using devices, test structures, detailed characterization, and modeling to quantify the sources of losses in state-of-the-art CdTe photovoltaic devices. Using this strategy and advanced synthesis, losses at the front interface, absorber, and rear interface were worked on in parallel. The final objective was to significantly improve the voltage deficit in CdTe devices to enable improvements in photovoltage and efficiency that can be implemented by industry in the near-term. Over the course of the project, the team developed new characterization techniques, analysis, and modeling which were then applied to state-of-the-art materials generated internally and collaboratively. In particular to enable rapid progress, NREL worked closely with First Solar where NREL grew complete devices as well as ones that interleaved process steps where First Solar had completed different steps such as absorber growth or absorber growth and activation using their baseline methods. Using detailed characterization and analysis including photoemission, photoluminescence, and scanning probe techniques enabled understanding of the loss pathways and area for improvements in our own and First Solar s materials. Ultimately, this contributed to the first series of new world record CdTe efficiencies since 2016, culminating in a 23.1% certified cell that was P-doped along with As-doped cells of similar performance. Internally, NREL improved the statistical variation in baseline As-doped devices and improved average photovoltage by over 100 mV. This was done through an improvement in absorber quality, changed front interface, and improved back contact. In addition to materially improving the fabrication processes at NREL, characterization, analysis, and modeling were developed and disseminated. NREL also played a pivotal role in community building over the course of this project working closely with the Cadmium Telluride Accelerator Consortium. NREL worked in a series of collaborations with academic and industry partners, leveraging knowledge and innovations from this project, as well as helped organize a series of workshops to ensure rapid progress in the field. Working closely with the academic community has led to a dissemination of knowledge; working with First Solar as increased US competitiveness First Solar expanded domestic production to ~10 GW and opened new facilities.

14 SOLAR ENERGY↗

Quantitative trait locus mapping combined with variant and transcriptome analyses identifies a cluster of gene candidates underlying the variation in leaf wax between upland and lowland switchgrass ecotypes

Switchgrass (Panicum virgatum L.) is a promising warm-season candidate energy crop. It occurs in two ecotypes, upland and lowland, which vary in a number of phenotypic traits, including leaf glaucousness. To initiate trait mapping, two F 2 mapping populations were developed by crossing two different F 1 sibs derived from a cross between the tetraploid lowland genotype AP13 and the tetraploid upland genotype VS16, and high-density linkage maps were generated. Quantitative trait locus (QTL) analyses of visually scored leaf glaucousness and of hydrophobicity of the abaxial leaf surface measured using a drop shape analyzer identified highly significant colocalizing QTL on chromosome 7K (Chr07K). Using a multipronged approach, we identified a cluster of genes including Pavir.7KG077009, which encodes a Type III polyketide synthase-like protein, and Pavir.7KG013754 and Pavir.7KG030500, two highly similar genes that encode putative acyl-acyl carrier protein (ACP) thioesterases, as strong candidates underlying the QTL. The lack of homoeologs for any of the three genes on Chr07N, the relatively low level of identity with other switchgrass KCS proteins and thioesterases, as well as the organization of the surrounding region suggest that Pavir.7KG077009 and Pavir.7KG013754/Pavir.7KG030500 were duplicated into a fast-evolving chromosome region, which led to their neofunctionalization. Furthermore, sequence analyses showed all three genes to be absent in the two upland compared to the two lowland accessions analyzed. This study provides an example of and practical guide for trait mapping and candidate gene identification in a complex genetic system by combining QTL mapping, transcriptomics and variant analysis.

59 BASIC BIOLOGICAL SCIENCES↗

Probing the potential of type V Deep eutectic solvents as sustainable electrolytes

The increasing interest within the scientific community in environmentally friendly solvents has led to a focus on Deep Eutectic Solvents (DES), which have natural components. DES are viewed as alternatives to traditional organic solvents and have the potential to be used as electrolytes. For the first time, transport properties of four Type V Deep Eutectic Salt Solutions (DESS) were accessed to investigate the potential of this technology, selecting precursors ranked as excellent in Eco-Scale metrics. The DESS were composed of terpene and trioctylphosphine oxide (TOPO), and varying concentrations of lithium bis(trifluoromethane)sulfonimide (LiTFSI), and their properties were assessed through self-diffusion, viscosity, density, and conductivity measurements. While Type V DESS are capable of dissolving significant amounts of LiTFSI (up to 30 % molar), their ionic conductivity is low, with values ranging from 3.6·10 –3 to 9.3·10 –2 mS·cm –1 at 25 °C, thus limiting their suitability as electrolytes, for instance, for lithium-ions batteries applications. Similar diffusion coefficients for Li + and TFSI – ions suggest the formation of long-lived ion pairs moving as a neutral species. As a result, future research aims to introduce additives to disrupt contact ion pairs and enhance transport properties, leveraging the sustainable appeal of DES and their use in advanced energy storage technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiocarbon Analyses Quantify Peat Carbon Losses With Increasing Temperature in a Whole Ecosystem Warming Experiment

Abstract Climate warming is expected to accelerate peatland degradation and release rates of carbon dioxide (CO 2 ) and methane (CH 4 ). Spruce and Peatlands Responses Under Changing Environments is an ecosystem‐scale climate manipulation experiment, designed to examine peatland ecosystem response to climate forcings. We examined whether heating up to +9 °C to 3 m‐deep in a peat bog over a 7‐year period led to higher C turnover and CO 2 and CH 4 emissions, by measuring 14 C of solid peat, dissolved organic carbon (DOC), CH 4 , and dissolved CO 2 (DIC). DOC, a major substrate for heterotrophic respiration, increased significantly with warming. There was no 7‐year trend in the DI 14 C of the ambient plots which remained similar to their DO 14 C. At +6.75 °C and +9 °C, the 14 C of DIC, a product of microbial respiration, initially resembled ambient plots but became more depleted over 7 years of warming. We attributed the shifts in DI 14 C to the increasing importance of solid phase peat as a substrate for microbial respiration and quantified this shift via the radiocarbon mass balance. The mass‐balance model revealed increases in peat‐supported respiration of the catotelm depths in heated plots over time and relative to ambient enclosures, from a baseline of 20%–25% in ambient enclosures, to 35%–40% in the heated plots. We find that warming stimulates microorganisms to respire ancient peat C, deposited under prior climate (cooler) conditions. This apparent destabilization of the large peat C reservoir has implications for peatland‐climate feedbacks especially if the balance of the peatland is tipped from net C sink to C source.

54 ENVIRONMENTAL SCIENCES↗

Concentrations and Health Implications of As, Hg, and Cd and Micronutrients in Rice and Emissions of CH 4 From Variably Flooded Paddies

Abstract The flooded soil conditions under which rice is typically grown are beneficial for boosting yield and decreasing herbicide inputs but may pose a food safety and environmental health risk. Flooded soils lead to reducing conditions and anaerobic metabolisms of soil microorganisms, which mobilizes arsenic from soil into soil solution, where it can be absorbed by rice roots and transported to grain. These conditions also promote the production and emission of methane (CH 4 )—a potent greenhouse gas. To evaluate how water management affects metal(loid) grain concentrations and CH 4 emissions, we conducted a 2‐year field study in which rice paddy water was managed under a range of soil redox conditions that spanned from flooded to non‐flooded. We observed that growing rice under less flooded conditions decreased CH 4 emissions and concentrations of grain total As, grain inorganic As, grain total Hg, and grain inorganic Hg relative to flooded conditions, with more reductions observed as conditions were drier; grain organic As and Hg (MeHg) species also decreased with drier conditions particularly in Year 1. However, the driest conditions tested led to a 50%–97% increase in grain Cd concentrations that exceeded the CODEX limit and grain yield reductions as high as 25% and 40% in Year 1 and 2, respectively. While concentrations of toxic metal(loid)s could be manipulated by water management, micronutrient concentrations were similar or decreased with drier conditions, potentially increasing grain Cd bioaccessibility to humans. Because practices for rice water management are gaining momentum, more research should monitor grain Cd levels along with micronutrients.

Environmental Sciences & Ecology↗

Bringing Alaska's Carbon Ore, Rare Earth, and Critical Minerals (CORE-CM) into Perspective

The final report outlines the outcomes of the Alaska CORE-CM Program, funded by the U.S. Department of Energy under award DE-FE0032050. Led by the University of Alaska Fairbanks and the Alaska Division of Geological and Geophysical Surveys, with assistance from other organizations, the project assessed Alaska's potential for Carbon Ore, Rare Earth Elements, and Critical Minerals (CORE-CM). Leveraging advanced analytical techniques, the project identified high-potential resource basins, evaluated geochemical and satellite data, and conducted targeted field investigations. Findings revealed promising concentrations of critical minerals in legacy samples and newly collected materials. The project also investigated innovative extraction technologies, including BioExtraction and use of supercritical CO2, which show significant promise for sustainable resource recovery. Additionally, the study explored the reuse of waste streams from active mining operations and coal byproducts such as using alkali-activated coal ash to manufacture concrete. Infrastructure and logistical challenges in Alaska’s remote regions are discussed, alongside strategies to establish a Technology Innovation Center aimed at advancing CORE-CM development in Alaska. The report includes actionable insights to support Alaska’s critical role in securing domestic supplies of essential minerals while addressing economic, environmental, and technological challenges.

01 COAL, LIGNITE, AND PEAT↗

Godzilla mineral dust and La Soufrière volcanic ash fallout immediately stimulate marine microbial phosphate uptake

During the “Godzilla” dust storm of June 2020, unusually high fluxes of mineral dust traveled across the Atlantic from the Sahara Desert, reaching the Caribbean Basin, Gulf Coast, and southeastern United States. Additionally, an eruption of the La Soufrière volcano on St. Vincent in April 2021 generated substantial ashfall in the southeastern Caribbean. While many studies have analyzed mineral dust’s ability to relieve nutrient limitation of phosphorus (P) in the P-stressed North Atlantic, less is known about the impact of extreme events and other natural aerosols on fluxes of P into seawater and from seawater into marine microbial cells. We quantified P and iron (Fe) content in mineral dust from the Godzilla dust storm and volcanic ash from the La Soufrière eruption collected at Ragged Point, Barbados. We also performed seawater incubations to assess the marine microbial response to aerosol deposition. Using environmentally-relevant concentrations of atmospheric particles for within the ocean’s mixed layer allowed us to draw realistic conclusions about how these deposition events impacted P cycling in situ. Volcanic ash has lower P content than mineral dust, and P in volcanic ash is far less soluble (~1%) than assumed in current atmospheric deposition models. Adding mineral dust and the volcanic ash leachate in concentrations representing different deposition scenarios increased soluble reactive phosphorus (SRP) concentrations in coastal seawater by ~7-32 nM. Phosphate uptake rate was stimulated in coastal seawater after either mineral dust or volcanic ash deposition at aerosol concentrations relevant to the Godzilla dust event, with ash eliciting the fastest uptake rate. Furthermore, high concentrations of both the mineral dust and volcanic ash led to slightly elevated alkaline phosphatase activity (APA) compared to the relevant controls, indicating higher potential for use of dissolved organic phosphorus (DOP) as a P source. Quantifying these aerosols’ impacts on P cycling is a significant step towards achieving a better understanding of their potential roles in relieving nutrient limitation and fueling the biological carbon pump.

54 ENVIRONMENTAL SCIENCES↗

Manipulating Organic Semiconductor Morphology with Visible Light

A method is presented to manipulate the final morphology of roll-to-roll slot-die coated poly(3-hexylthiophene) (P3HT) by optically exciting the p-type polymer in solution while coating. These results provide a comprehensive picture of the entire knowledge chain, from demonstrating how to apply the authors’ method to a fundamental understanding of the changes in morphology and physical properties induced by exciting P3HT while coating. By combining results from density functional theory and molecular dynamics simulations with a variety of X-ray experiments, absorption spectroscopy, and THz spectroscopy, the relationship between morphology and physical properties of the thin film is demonstrated. Specifically, in P3HT films excited with light during deposition, changes in crystallinity and texture with more face-on orientation and increased out-of-plane charge mobility are observed.

36 MATERIALS SCIENCE↗

Influence of the molecular weight and size distribution of PSS on mixed ionic-electronic transport in PEDOT:PSS

The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition–fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow (D = 1.1) and broad (D = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS (Mn = 145 kg mol –1 ) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [μC*] values (~140 F cm –1 V –1 s –1 ) in PEDOT:PSS, despite having a lower volumetric capacitance (C* = 35 ± 4 F cm –3 ). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility (μOECT ~4 cm 2 V –1 s –1 ) and hence transconductance. Furthermore, these studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–Organic Frameworks for C6 Alkane Separation

The separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal-organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Lastly, we briefly discuss the existing challenges, possible solutions, and future directions of this important field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗