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At least 163 records · Page 9

Effects of film thickness on electrochemical properties of nanoscale polyethylenedioxythiophene (PEDOT) thin films grown by oxidative molecular layer deposition (oMLD)

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. In conclusion, these insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling PET oligomers vs monomers via microwave-induced heating and swelling

The production of polyethylene terephthalate (PET) bottles and fibers, and their subsequent mismanagement, have created an urgent need to develop strategies to handle the resulting waste. Here, in this work, glycolysis of PET using manganese oxide catalysts under microwave-assisted heating is demonstrated to form oligomers and the monomer bis(2-hydroxyethyl) terephthalate (BHET) at moderate conditions. Higher surface area catalysts achieve faster overall rates of depolymerization to the monomer. Oligomers form homogeneously and depolymerize to monomers over manganese oxide. The polymer-to-solvent ratio and reaction temperature affect the overall oligomer yield. The swelling of PET, caused by the diffusion of ethylene glycol into the polymer matrix, causes the dissolution of the PET to form oligomers. Oligomers are characterized and show similar physical properties to the starting PET despite having 1/20th of the molecular weight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AI‐Accelerated Optimization of Self‐Assembled Organic Mixed Ionic‐Electronic Conductors (OMIEC) (Final Report)

This document describes research activities, products and outcomes of a DOE-funded program to help accelerate development of Organic Mixed Ionic Electronic Conductors (OMIECs) using neutron scattering and high-throughput experimentation. OMIECs are organic materials that conduct both ionic and electronic charge carriers. For these new OMIEC materials, self-assembling ion-conducting block copolymers (BCPs) are used as a structural template for electronic conducting polymers. This forms OMIECs with long-range structural order that can help facilitate long-range electronic transport. The conductive properties of OMIECs are closely associated with their structure, which is affected by solution conditions and polymer macromolecular designs. Thus high-throughput experimentation has been implemented to explore this large design space effectively. The BCP-CP OMIEC systems explored are composed of ion-conducting diblock or triblock copolymers containing polyethylene oxide (PEO), di(ethylene glycol) ethyl ether acrylate (DEGEEA) or poly(ethylene glycol) methyl ether acrylate) (PEGMEA) hydrophilic blocks. These blocks will be coupled with either polypropylene oxide (PPO) or polyheptafluorobutyl acrylate (PHFBA) hydrophobic blocks to drive assembly. The electronic conducting component consists of several different types of conjugated polymers. Small angle scattering of neutrons and X-rays (SANS/SAXS) as well as electrochemical analysis have been coupled with modern algorithms for autonomous research using artificial intelligence (AI).

36 MATERIALS SCIENCE↗

Block copolymer-mediated synthesis of TiO2/RuO2 nanocomposite for efficient oxygen evolution reaction

Abstract An amphiphilic block copolymer, poly (styrene-2-polyvinyl pyridine-ethylene oxide), was used as a structure-directing and stabilizing agent to synthesize TiO 2 /RuO 2 nanocomposite. The strong interaction of polymers with metal precursors led to formation of a porous heterointerface of TiO 2 /RuO 2 . It acted as a bridge for electron transport, which can accelerate the water splitting reaction. Scanning electron microscopy, energy-dispersive X -ray spectroscopy, transmission electron microscopy, and X -ray diffraction analysis of TiO 2 /RuO 2 samples revealed successful fabrication of TiO 2 /RuO 2 nanocomposites. The TiO 2 /RuO 2 nanocomposites were used to measure electrochemical water splitting in three-electrode systems in 0.1-M KOH. Electrochemical activities unveil that TiO 2 /RuO 2 -150 nanocomposites displayed superior oxygen evolution reaction activity, having a low overpotential of 260 mV with a Tafel slope of 80 mVdec −1 . Graphical abstract

36 MATERIALS SCIENCE↗

Design and Characterization of Hybrid Multilayer Structures: Layer-by-Layer Growth of Polymer and Graphene Oxide Assemblies and Their Utility in Fuel Cell Applications

We report the layer-by-layer growth of poly- (ethylenimine) (PEI) that has been modified with sulfamate functionalities (S-PEI) using Zr 4+ -complexation interlayer linking chemistry. We have also deposited adlayers of graphene oxide (GO) that have been modified to possess sulfate functionalities (SGO), onto the S-PEI layers. The multilayer assemblies are formed with sulfamate/sulfate and sulfate/sulfate (S-PEI + S-GO) interlayer linking chemistry. In all cases the adlayer thickness is consistent with predictions based on van der Waals volume and/or molecular mechanics calculations. X-ray photoelectron spectroscopy (XPS) is used to characterize the Zr/S stoichiometry in the multilayer assembly. The utility of these hybrid multilayer structures is demonstrated in a Proton Exchange Membrane (PEM) fuel cell, where they are shown to reduce H 2 gas crossover by 15% with only a 12 nm thick layer.

fuel cell↗

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic–inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m 2 g −1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

Chemistry↗

Cation–polymer interactions and local heterogeneity determine the relative order of alkali cation diffusion coefficients in PEGDA hydrogels

Current research efforts are focused on endowing polymer membranes with ion–ion selectivity by incorporating ion–polymer interactions into materials to bias the selective partitioning and or diffusivity of one species over another. However, little is known about the impact of such interactions on the mechanisms of ion transport. In this study, we probe the influence of cation–polymer interactions on cation, anion, and salt diffusivity in a model membrane material, poly(ethylene glycol) diacrylate (PEGDA) by modeling concentrated polyethylene oxide solutions via molecular dynamics simulations. These results are compared to published experimental data for LiCl, NaCl, and KCl diffusion in PEGDA. Experimentally, the order of salt and cation diffusion coefficients for LiCl, NaCl, and KCl deviate from the order in aqueous solutions. Here, simulations identify these deviations to arise from cation–polymer coordination in the membrane. Both the fraction of bound cations and the average binding lifetime increases with decreasing cation hydration free energy (moving down the alkali series), leading to different diffusivity trends in the membrane compared to solution. However, to recover the experimentally observed order of diffusivities cations and salt in our simulations, we needed to incorporate membrane heterogeneity explicitly via a polymer charge scaling procedure. Together, our results indicate that cation–polymer interactions, as well as spatial heterogeneity within the membrane, play a critical role in dictating the observed order of alkali cation and salt diffusion coefficients in membranes.

36 MATERIALS SCIENCE↗

Hydrogen bonds enhanced composite polymer electrolyte for high-voltage cathode of solid-state lithium battery

Polymer electrolyte is one of the important components for developing advanced solid-state lithium batteries (SSLBs). However, the narrow electrochemical stability window restricts the practical application with high-voltage cathodes. In this study, a series of composite solid electrolytes (CSEs), possessing both wide electrochemical stability window (up to 5.0 V vs. Li + /Li) and high ionic conductivity (over 1.35×10 -3 S/cm at 25 °C), were reported by integrating SiO 2 nanoparticles into poly(vinyl ethylene carbonate) polymer electrolyte. The enhanced anti-oxidation performances are mainly caused and confirmed by the local intermolecular interactions of hydrogen bonds in CSE. Based on this CSE, the SSLBs with LiCoO 2 cathode present good cycle stability at high voltage, and the capacity retention with 4.5 V cut-off voltage is about 94% after 200 cycles. This work not only proves the importance of intermolecular interactions in CSE, but also provides an effective method for achieving high-energy SSLBs with enhanced interface compatibility between polymer electrolyte and highvoltage cathodes

25 ENERGY STORAGE↗

Lignin-Derived Methoxyterephthalates for Performance-Advantaged Polymers and Plasticizers

Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.

09 BIOMASS FUELS↗

A high throughput assay to detect enzymatic polyethylene oxidation

Biological plastics deconstruction and upcycling have emerged as sustainable alternatives to traditional recycling technologies for plastics waste. The discovery and engineering of efficient thermostable poly(ethylene terephthalate) (PET) hydrolases have made biological PET recycling possible at scale; however, enzymes for non-PET plastics, which account for approximately 70% of all plastics produced, remain largely undiscovered. To accelerate the discovery of such enzymes, we develop a high-throughput screen to detect initial polymer oxidation, specifically that of the C-H bond to an aldehyde. We test 4-hydrazino-7-nitro-2,1,3-benxoxadiozole hydrazine (NBD-H), which reacts with generated aldehydes to form a fluorescent hydrazone on plasma oxidized low-density polyethylene (LDPE) films. Hydrazone generation correlated well with the area of aldehyde peaks as measured by Fourier Transform Infrared Spectroscopy (FTIR) (R2 = 0.92). Moreover, we demonstrate that the probe reliably identifies LDPE-active dye decolorizing peroxidases (DyPs) that generate aldehydes on LDPE films (1.7 – 3.0 fold change relative to background), serving as an effective screen as demonstrated by receiver operating characteristic area under the curve of 0.95. Furthermore, this assay offers an LDPE oxidation screening platform that can be readily parallelized and automated for accelerated discovery of enzymes involved in polyolefin deconstruction.

biocatalysis↗

Hairy nanoparticles by atom transfer radical polymerization in miniemulsion

Polymer nanoparticles with various architectures and functionalities are promising materials in numerous fields. Miniemulsion polymerization is one of the suitable pathways to prepare polymer nanoparticles since each droplet could act as a “nanoreactor”. A “smart” atom transfer radical polymerization (ATRP) catalytic system comprising Cu-TPMA/DS – (TPMA = tris(2-pyridylmethyl)amine, DS – = dodecyl sulfate anion) ion pair catalyst was efficiently applied in miniemulsion ATRP at low catalyst concentrations. Herein, hairy nanoparticles consisting of hydrophobic poly(n-butyl methacrylate) (P(BMA/EGDMA), EGDMA = ethylene glycol dimethacrylate) network “core” and hydrophilic oligo(ethylene oxide) methyl ether methacrylate (OEOMA) chains as “hair” were prepared by miniemulsion ATRP and a successive chain extension by aqueous ATRP from the particle surface. The addition of an inimer, 2-(α-bromoisobutyryloxy)ethyl methacrylate (HEMA-iBBr) to the P(BMA/EGDMA) network introduced more ATRP initiation sites for ATRP of OEOMA, enabling adjustment of the particle size from >400 nm to <150 nm. The miniemulsion system remained stable after the one pot synthesis of P(BMA/EGDMA)-g-POEOMA and P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA, and the resulting polymer nanoparticles were re-dispersed in water for further modification. A zwitterionic monomer, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was grafted from P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA. The resulting hairy nanoparticles provide an avenue for the design and preparation of novel nanostructured materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facilitated transport membrane with functionalized ionic liquid carriers for CO 2 /N 2 , CO 2 /O 2 , and CO 2 /air separations

CO 2 separations from cabin air and the atmospheric air are challenged by the very low partial pressures of CO 2 . In this study, a facilitated transport membrane (FTM) is developed to separate CO 2 from air using functionalized ionic liquid (IL) and poly(ionic liquid) (PIL) carriers. A highly permeable bicontinuous structured poly(ethersulfone)/poly(ethylene terephthalate) ( b PES/PET) substrate is used to support the PIL–IL impregnated graphene oxide thin film. The CO 2 separation performance was tested under a mixture feed of CO 2 /N 2 /O 2 /H 2 O. Under 410 ppm of CO 2 at 1 atm feed gas, CO 2 permanence of 3923 GPU, and CO 2 /N 2 and CO 2 /O 2 selectivities of 1200 and 300, respectively, are achieved with helium sweeping on the permeate side. For increased transmembrane pressure (>0 atm), a thicker PIL–IL/GO layer was shown to provide mechanical strength and prevent leaching of the mobile carrier. CO 2 binding to the carriers, ion diffusivities, and the glass transition temperature of the PIL–IL gels were examined to determine the membrane composition and rationalize the superior separation performance obtained. This report represents the first FTM study with PIL–IL carriers for CO 2 separation from air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photostability of Ambient-Processed, Conjugated Polymer Electrochromic Devices Encapsulated by Bioderived Barrier Films

Polymer-based electrochromic devices (ECDs) are a promising technology for enabling low-voltage, disposable displays, yet are currently limited by photo-oxidative bleaching of the active materials. Here, renewable barrier films composed of cellulose and chitin are presented as an alternative to poly(ethylene terephthalate) (PET) for encapsulating ECDs. To assess barrier film effectiveness, lateral ECDs composed of poly(3,4-propylenedioxythiophene-(CH 2 OEtHx) 2 ) (P(ProDOT)) active layers were constructed and encapsulated with a multilayer barrier consisting of chitin nanofibers and cellulose nanocrystals spray cast onto a cellulose acetate substrate (oxygen transmission rate (OTR) = 29 cm 3 m –2 day –1 ), a commercially available PET film (OTR = 8.5 cm 3 m –2 day –1 ), and a high-performance PET-Al 2 O 3 multilayer barrier film (OTR < 1 cm 3 m –2 day –1 ). The photodegradation of the P(ProDOT) active layer was determined by measuring the evolution of the colorimetric contrast (ΔE*) and switching speeds as a function of light exposure (100 mW cm –2 , AM 1.5 G light). Photodegradation was found to proceed at a similar rate for all encapsulated devices (roughly 10 times more slowly than unencapsulated devices), highlighting the opportunity for replacing petroleum packaging with bioderived barrier films. Analysis of the switching kinetics, the shifts in optical absorbance, and evidence of chemical degradation indicate that both photochemical breakdown of the electrolyte and cross-linking of the P(ProDOT) active material are key drivers for loss of device performance when oxygen flux to the active material is limited. Furthermore, pathways toward better understanding photodegradation are then proposed with sustainability in mind for future ECD design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quasi-elastic neutron scattering study on dynamically asymmetric polymer blends

Compatibility between polymers with different glass transition temperatures controls the thermomechanical properties of blends. This work explores the segmental dynamics of poly(methyl acrylate) (PMA) chains when they are blended with polymers of different rigidities and miscibility. Inspired by the intriguing dynamic asymmetry of chains within the interfacial layer of nanoparticles, this study aims to understand dynamic heterogeneity in dynamically asymmetric blends of PMA/poly(methyl methacrylate) (PMMA), PMA/polystyrene (PS), and PMA/poly(ethylene oxide) (PEO) using the differential scanning calorimetry (DSC) and quasi-elastic neutron scattering (QENS) measurements below and above the glass transition temperature of PMMA or PS. Further, results revealed that the segmental jump distance of PMA increased on blending due to volume enhancement. The reduced effective diffusivity of PMA in PMMA is attributed to PMMA's enhanced flexibility (lower characteristic ratio, C ∞ ) and superior interaction (lower ) when compared with the PS environment. The results demonstrate that the chain rigidity and miscibility affect the free volume, interchain cooperativity, and segmental dynamics in dynamically asymmetric blends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailored polyMOFs for ion transport in lithium-based battery electrolyte

Owing to their low flammability, solid-state and quasi-solid-state electrolytes are safer alternatives to liquid organic electrolytes for energy storage applications. Metal–organic frameworks (MOFs), with facile functional tunability, long-range order, and rich host–guest interactions, have been implemented as electrolyte materials in a wide range of energy storage applications. In this work, we investigate a class of MOFs called polyMOFs as quasi-solid-state electrolyte materials. Unlike MOF–polymer composites, which are physical mixtures of MOF particles and polymers, polyMOFs are composed of polymeric linkers and metal ion nodes that self-assembled into crystalline and porous framework materials. PolyMOFs thus marry the ionic transport properties of liquid electrolyte and polymers with the synthetic versatility and host–guest interactions of MOFs. We demonstrate that the functionality of the polymer backbone of the polyMOF linker can improve room-temperature ion transport in the material. The polyMOF based on poly(ethylene glycol) (PEG) exhibits greater ionic conductivity, lithium transference number, and lower activation energy than its polyethylene (PE) analog. Supported by solid-state 7 Li nuclear magnetic resonance spectroscopy, we propose these improvements are due to stronger coordination of Li + to oxide sites in PEG, allowing for dissociation of Li and its associated anion. DFT studies further reveal that the confined solvent molecule mediates Li + transport in PEG-functionalized UiO-66 via a metastable adsorption and hopping mechanism. This work lies at the interface of inorganic and polymer electrolytes, unveiling fundamental insights into the design of next-generation ion conductive materials for energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyelectrolyte Surface Diffusion in a Nanoslit Geometry

The surface diffusion of poly-l-lysine (PLL) in a planar nanoslit was studied using convex lens-induced confinement (CLiC) single-molecule tracking microscopy. Here, three surface chemistries were employed to understand the interplay of electrostatic and short-range interactions: an amine-functionalized silica surface, an oligo(ethylene oxide) (OEG)-modified surface, and a 1:1 mixture of the two ligands. Effective surface diffusion coefficients increased rapidly with slit height until saturating for slit heights <30 nm. While diffusion at a semi-infinite interface was significantly faster for OEG surfaces, the diffusion coefficient increased most rapidly with slit height for amine-functionalized surfaces, resulting in surface diffusion within very thin slits being nearly independent of surface chemistry. Intermittent random walks were simulated within a planar slit geometry, using experimentally measured parameters obtained from diffusion at a single interface to account for the characteristic short-range interactions between PLL and each surface chemistry, and were in good agreement with experimental measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facilitated Transport Membranes with Tunable Amine-CO 2 Chemistry for CO 2 /H 2 Separation

CO 2 -selective, amine-containing facilitated transport membranes are of great interest for syngas purification since high-pressure H 2 can be retained upon CO 2 removal. A variety of amine-containing polymers have shown decent chemical and thermal stability at aggressive conditions, but their CO 2 /H 2 separation properties are largely limited by the hydrostatic compaction and severe carrier saturation associated with the high syngas pressure. Herein, we report a new approach to enhance the CO 2 permeability by manipulating the steric hindrance of the amine carriers. A series of α-aminoacids with different alkyl or hydroxyethyl substituents are deprotonated by 2-(1-piperazinyl)ethylamine, leading to nonvolatile amine carriers with different degrees of steric hindrance. For hosting the low MW amine carriers, a highly crosslinked poly(vinyl acetal) is synthesized as a water-swellable polymer network. In order to avoid membrane compaction, perforated graphene oxide mono-sheets are dispersed as reinforcement fillers. In the presence of moisture, a bulkier alkyl substituent to the amino site (increasing steric hindrance) destabilizes the carbamate adduct and thus drastically increases the chemisorption of CO 2 , while the incorporation of ethylene oxide groups provides additional physisorption of CO 2 . The enhanced CO 2 solubility significantly mitigates the carrier saturation behavior, and an unprecedented CO 2 /H 2 selectivity greater than 100 is demonstrated at 107 °C and 12.5 atm of CO 2 partial pressure. As the CO 2 partial pressure reduces to 0.4 atm, a less hindered amine yields a higher reactive diffusivity of CO 2 , resulting in a CO 2 permeance of 435 GPU with a selectivity greater than 500. These reaction-mediated polymeric membranes are well above the theoretical upper bound, and they are of great interest for designing a highly-selective membrane process for syngas purification.

08 HYDROGEN↗