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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

2,4,6‐Triphenylpyridinium: A Bulky, Highly Electron‐Withdrawing Substituent That Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Abstract The reactivity of Ni II and Pd II olefin polymerization catalysts can be enhanced by introduction of electron‐withdrawing substituents on the supporting ligands rendering the metal centers more electrophilic. Reported here is a comparison of ethylene polymerization activity of a classical salicyliminato nickel catalyst substituted with the powerful electron‐withdrawing 2,4,6‐triphenylpyridinium (trippy) group to the ‐CF 3 analogue. The trippy substituent is substantially more electron‐withdrawing (σ meta =0.63) than the trifluoromethyl group (σ meta =0.43) which results in a ca. 8‐fold increase in catalytic turnover frequency. An additional advantage of trippy is the high steric bulk relative to the trifluoromethyl group. This feature results in a four‐fold increase in polymer molecular weight owing to enhanced retardation of chain transfer. A significant increase in catalyst lifetime is observed as well.

Janeta, Mateusz↗
DOE OSTI2025

Soft and Stretchable Thienopyrroledione–Based Polymers via Direct Arylation

π-conjugated polymers (CPs) that are concurrently soft and stretchable are needed for deformable electronics. Molecular-level modification of indacenodithiophene (IDT) copolymers, a class of CPs that exhibit high hole mobilities (μ hole ), is an approach that can help realize intrinsically soft and stretchable CPs. Numerous examples of design strategies to adjust the stretchability of CPs exist, but imparting softness is comparatively less studied. In this study, a systematic molecular weight (MW) series is constructed on a promising candidate for soft CPs, poly(indacenodithiophene-co-thienopyrroledione) (p(IDT C16- TPD C8 )), by optimizing direct arylation polymerization conditions in hopes of improving stretchability and μhole without significantly impacting softness. We found p(IDT C16- TPD C8 ) at a degree of polymerization of 32 shows high stretchability (crack onset strain, CoS > 100%) without significantly impacting softness (elastic modulus, E = 32 MPa), which to the best of our knowledge outperforms previously reported stretchable and soft CPs. To further study how molecular-level modifications impact polymer properties, a MW series of a new extended donor unit polymer, poly(indacenodithienothiophene-co-thienopyrroledione) (p(IDTT C16- TPD C8 )), was synthesized. The IDTT C16 copolymers did not result in a greater average μ hole when comparing between p(IDTT C16- TPD C8 ) and p(IDT C16- TPD C8 ) despite their higher crystallinity observed by GIWAXS. While these findings warrant further investigation, this study points toward unique charge transport properties of IDT-based polymers.

direct arylation polymerization↗
DOE OSTI2021

Experimental observation of hydrocarbon growth by resonance stabilized radical-radical chain reaction

Rapid molecular weight growth of hydrocarbons occurs in flames, in industrial synthesis, and potentially in cold astrochemical environments. A variety of high- and low-temperature chemical mechanisms have been proposed and confirmed, but more facile pathways may be needed to explain observations. Here, we provide laboratory confirmation in a controlled pyrolysis environment of a recently proposed mechanism, radical-radical chain reactions of resonance-stabilized species. The recombination reaction of phenyl (c-C 6 H 5 ) and benzyl (c-C 6 H 5 CH 2 ) radicals produces both diphenylmethane and diphenylmethyl radicals, the concentration of the latter increasing with rising temperature. A second phenyl addition to the product radical forms both triphenylmethane and triphenylmethyl radicals, confirming the propagation of radical-radical chain reactions under the experimental conditions of high temperature (1100-1600 K) and low pressure (~3 kPa). Similar chain reactions may contribute to particle growth in flames, the interstellar medium, and industrial reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

The reactivity of Ni(II) and Pd(II) olefin polymerization catalysts can be enhanced by introduction of electron-withdrawing substituents on the supporting ligands rendering the metal centers more electrophilic. Reported here is a comparison of ethylene polymerization activity of a classical salicyliminato nickel catalyst substituted with the powerful electron-withdrawing 2,4,6-triphenylpyridinium (trippy) group to its’ –CF3 analog. The trippy substituent is substantially more electron-withdrawing (σmeta = 0.63) than the trifluoromethyl group (σmeta = 0.43) which results in a ca. 8-fold increase in catalytic turnover frequency. An additional advantage of trippy is its’ high steric bulk relative to the trifluoromethyl group. This feature results in a four-fold increase in polymer molecular weight due to enhanced retardation of chain transfer. Here, a significant increase in catalyst lifetime is observed as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Experimental Observation of Hydrocarbon Growth by Resonance‐Stabilized Radical–Radical Chain Reaction

Abstract Rapid molecular‐weight growth of hydrocarbons occurs in flames, in industrial synthesis, and potentially in cold astrochemical environments. A variety of high‐ and low‐temperature chemical mechanisms have been proposed and confirmed, but more facile pathways may be needed to explain observations. We provide laboratory confirmation in a controlled pyrolysis environment of a recently proposed mechanism, radical–radical chain reactions of resonance‐stabilized species. The recombination reaction of phenyl (c‐C 6 H 5 ) and benzyl (c‐C 6 H 5 CH 2 ) radicals produces both diphenylmethane and diphenylmethyl radicals, the concentration of the latter increasing with rising temperature. A second phenyl addition to the product radical forms both triphenylmethane and triphenylmethyl radicals, confirming the propagation of radical–radical chain reactions under the experimental conditions of high temperature (1100–1600 K) and low pressure (ca. 3 kPa). Similar chain reactions may contribute to particle growth in flames, the interstellar medium, and industrial reactors.

Couch, David E.↗
DOE OSTI2025

Accelerated Self-Healing and Property Recovery in Brush Particle Solids Featuring Brush Dispersity

Brush particles, hybrid materials consisting of polymer chains tethered to particle surfaces, offer tunable properties that make them promising candidates for advanced functional materials. This study investigated the role of chain dispersity in the viscoelastic self-healing of poly (methyl acrylate) (PMA)-based brush particle solids. Increasing the molecular weight dispersity of grafted chains significantly enhanced both strain-to-fracture and toughness of brush particle solids, while the elastic modulus and glass transition temperature were independent of chain dispersity. Cut-and-adhere testing revealed a significant acceleration of the rate of toughness recovery in high-dispersity systems as compared to low-dispersity analogs for which toughness recovery markedly lagged the recovery of Young’s modulus. The results suggest that structure and property recovery in brush particle solids are sensitive to the dynamical heterogeneity of brush canopies and highlight the role of molecular weight dispersity as a design parameter to enable hybrid materials with advanced self-healing ability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Evaluation of adsorption and mechanical strength of 13X zeolite mixtures with phyllosilicate binders using molecular dynamics simulation and positron annihilation spectroscopy

There is growing interest in developing zeolites with novel internal structures that have optimal adsorptive capacity and high mechanical strength, while offering advantages, such as being light weight. We integrate computational and experimental methods to explore the effect of binder/zeolite types, and weight percentages on the mechanical strength of 13X zeolite and adsorption capacities of N 2 , H 2 O, and CO 2 for additive manufacturing (AM) applications with the goal of maximizing both adsorption and strength. Zeolite 13X mixtures and phyllosilicate binders (either bentonite or kaolin) are combined using molecular dynamics (MD) simulations to create structures with various binder/zeolite weight percentages. Further, adsorption capabilities and mechanical strength are assessed using the grand canonical Monte Carlo (GCMC) and ReaxFF modules, respectively. Our modeling shows that an optimized zeolite/binder ratio for N 2 adsorption is around 15 wt% for kaolin and roughly 10 wt% for bentonite. The resulting parameters can be applied to facilitate macro-scale computational fluid dynamics (CFD) and finite element method (FEM) simulations of an AM zeolite structure. We also performed Positron Annihilation Lifetime Spectroscopy (PALS) measurements on zeolite samples to explore the effect of changes in the internal volume. The results show an inverse relationship between the free volume and the solid loading and adding a binder changes the morphology of the zeolite-binder compound and decreases open-volume area significantly.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Chemical Recycling of Carbon Fiber-Reinforced Nylon Composites

Nylon-based fiber-reinforced composites are widely used in various sectors due to their strength, durability, and lightweight properties. Despite their widespread use, recycling these composites is difficult due to the inability to separate fibers and thermal instability of nylon at high temperatures. Consequently, most nylon composites are landfilled, leading to significant economic loss. Current fiber recovery methods (i.e., pyrolysis) are energetically inefficient and preclude recovery of the matrix. Dissolution methods, such as using hexafluoroisopropanol (HFIP), allow recovery of polymer and fiber but are economically taxing and require extensive safety infrastructure. Herein we report tailored glycolysis of nylon-6 composites, resulting in separated constituent fibers and nylon-6 oligomers. Deconstruction kinetics reveal nylon’s molecular weight reductions from 32,600 to 2000 g/mol, while SEM and tensile testing confirm recovered fiber integrity. In conclusion, this approach offers a pathway to reclaim high-value materials from nylon composites, providing a strategy for the chemical recycling of fiber-reinforced composites.

Zheng, Jackie [Univ. of Tennessee, Knoxville, TN (↗
DOE OSTI2021

Measurement report: Cloud condensation nuclei activity and its variation with organic oxidation level and volatility observed during an aerosol life cycle intensive operational period (ALC-IOP)

Abstract. Cloud condensation nuclei (CCN) spectrum and the CCN activated fraction of size-resolved aerosols (SR-CCN) were measured at a rural site on Long Island during the Department of Energy (DOE) aerosol life cycle intensive operational period (ALC-IOP) from 15 July to 15 August 2011. During the last week of the ALC-IOP, the dependence of the activated fraction on aerosol volatility was characterized by sampling downstream of a thermodenuder (TD) operated at temperatures up to 100 ∘C. Here we present aerosol properties, including aerosol total number concentration, CCN spectrum, and the CCN hygroscopicity, for air masses of representative origins during the ALC-IOP. The hygroscopicity of organic species in the aerosol is derived from CCN hygroscopicity and chemical composition. The dependence of organic hygroscopicity on the organic oxidation level (e.g., atomic O:C ratio) agrees well with theoretical predictions and results from previous laboratory and field studies. The derived κorg and O:C ratio first increase as TD temperature increases from 20 ∘C (i.e., ambient temperature) to 50 or 75 ∘C and then decrease as TD temperature further increases to 100 ∘C. The initial increases of O:C and κorg with TD temperature below 50 ∘C are likely due to evaporation of more volatile organics with relatively lower O:C and hygroscopicity such as primary organic aerosol. At the high TD temperatures, the decreases of O:C and κorg indicate that evaporated organics were more oxygenated and had lower molecular weights. These trends are different from previous laboratory experiments and field observations, which reported that organic O:C increased monotonically with increasing TD temperature, whereas κorg decreased with the TD temperature. One possible reason is that previous studies were either focused on laboratory-generated secondary organic aerosol (SOA) or based on field observations at locations more dominated by SOA.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Using Nanofiller Assemblies to Control the Crystallization Kinetics of High-Density Polyethylene

Polyethylene-grafted nanoparticles (NPs) are organized into a variety of assemblies in a polydisperse polyethylene melt by tailoring the graft density and molecular weights of the graft chains. Under these conditions we systematically vary NP assemble state and study is consequences on crystal nucleation and growth rates. We find that the nucleation rate is suppressed below that of the unfilled polymer for good NP spatial dispersion. However, poorer dispersion, which leads to the formation of NP assemblies, can accelerate nucleation likely by providing multiple heterogenous sites due to topographical features. We find that a key parameter, the chain overcrowding in the brush, can predict these nucleation trends – in this language, the most enhanced nucleation rate is found when the grafts are the most overcrowded, and hence the least interpenetrated with the matrix chains. This result is consistent with one other literature result which utilized short crystallizable polyethylene glycol grafts in short PEO matrices. The growth kinetics were retarded for all nanocomposites, their temperature dependences were essentially equal to that for the pure polymer (in the absence of NPs) – the NPs thus do not affect secondary nucleation, indicating that the transport of the matrix to the growth front is the rate determining step. Thus, evidently the increase in matrix viscosity, or reduction in growth rates, is directly determined by the agglomeration state of the NPs. These results are consistent with past works with bare silica NPs in PEO, and with silica NPs grafted with amorphous chains in a PEO matrix, suggesting that growth kinetics in these systems apparently follow “universal” behavior. Additionally, there are initial hints that the ratio of the effective surface area of the NP clusters per unit matrix volume provides a unified description of the NP induced confinement that slows growth kinetics. Furthermore, our work thus shows that there is an evolving understanding of the role of NPs on crystallization kinetics, in particular crystal growth where trends appear to be independent of the grafts ability to crystallize.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A Deep Neural Network for Accurate and Robust Prediction of the Glass Transition Temperature of Polyhydroxyalkanoate Homo- and Copolymers

The purpose of this study was to develop a data-driven machine learning model to predict the performance properties of polyhydroxyalkanoates (PHAs), a group of biosourced polyesters featuring excellent performance, to guide future design and synthesis experiments. A deep neural network (DNN) machine learning model was built for predicting the glass transition temperature, Tg, of PHA homo- and copolymers. Molecular fingerprints were used to capture the structural and atomic information of PHA monomers. The other input variables included the molecular weight, the polydispersity index, and the percentage of each monomer in the homo- and copolymers. The results indicate that the DNN model achieves high accuracy in estimation of the glass transition temperature of PHAs. In addition, the symmetry of the DNN model is ensured by incorporating symmetry data in the training process. The DNN model achieved better performance than the support vector machine (SVD), a nonlinear ML model and least absolute shrinkage and selection operator (LASSO), a sparse linear regression model. The relative importance of factors affecting the DNN model prediction were analyzed. Sensitivity of the DNN model, including strategies to deal with missing data, were also investigated. Compared with commonly used machine learning models incorporating quantitative structure–property (QSPR) relationships, it does not require an explicit descriptor selection step but shows a comparable performance. The machine learning model framework can be readily extended to predict other properties.

quantitative structure–property relationship (QSPR↗
DOE OSTI2021

A New Approach to Fundamental Mechanism Discovery in Polymer Upcycling

We present a new experimental methodology for detailed experimental investigations of depolymerization reactions over solid catalysts. This project aims to address a critical need in fundamental research on chemical upcycling of polymers – the lack of rapid, sensitive, isomerselective probing techniques for the detection of reaction intermediates and products. Our method combines a heterogeneous catalysis reactor for the study of multiphase (gas/polymer melt/solid) systems, coupled to a vacuum UV photoionization time-of-flight mass spectrometer. This apparatus draws on our expertise in probing complex gas-phase chemistry and enables highthroughput, detailed chemical speciation measurements of the gas phase above the catalyst, providing valuable information on the heterogeneous catalytic reactions. Using this approach, we investigated the depolymerization of high-density polyethylene (HDPE) over Ir-doped zeolite catalysts. We showed that the product distribution was dominated by low-molecular weight alkenes with terminal C=C double bonds and revealed the presence of many methyl-substituted alkenes and alkanes, suggesting extensive methyl radical chemistry. In addition, we investigated the fundamental reactivity of model oligomer molecules n-butane and isobutane over ZSM-5 zeolites. We demonstrated the first direct detection of methyl radical intermediates, confirming the key role of methyl in zeolite-catalyzed activation of alkanes. Our results show the potential of this experimental method to achieve deep insight into the complex depolymerization reactions and pave the way for detailed mechanistic studies, leading to increased fundamental understanding of key processes in chemical upcycling of polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Competing Effects of Network Architecture and Composition on Polydomain Liquid Crystal Elastomers

Main-chain liquid crystal elastomers (LCEs) are synthesized to investigate the interplay of the composition and network structure on LCE nematic-to-isotropic (N–I) transitions. We focus on networks synthesized from liquid crystalline oligomers reacted with tri- or tetrafunctional nonmesogenic cross-linker molecules. We find that coupling between mesogens and the polymer backbone increases with the degree of cross-linking. However, this enhanced coupling competes with mesogenic dilution arising from the cross-linker molecules to determine the N–I transition temperature (T NI ). When cross-linker molecules are dilute, the degree of cross-linking directly correlates to the change in T NI from the oligomer to LCE (ΔT NI ) through mesogen–backbone coupling. In this regime, ΔT NI ranges from 2.9 to 12.2 °C and 2.9–13.9 °C for tri- and tetrafunctional cross-linkers, respectively. At high cross-linker concentrations, deviations from this linear relationship appear. Further, the fractional mesogen content within an oligomer chain induces molecular weight-dependent mesogenic dilution effects arising from the flexible spacer molecules. Analysis of the N–I transition peak reveals a maximum latent heat per gram of mesogen (ΔH NI,mes ) for this system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Role of Polymer Architecture in CO 2 Capture from Air Using Supported Poly(alkylenimine)s: Linear vs Branched Polymers

Direct air capture (DAC) of CO 2 coupled with geologic storage is a promising climate change mitigation strategy, with some applications employing amines supported on porous solids as CO 2 sorbents. While branched poly(ethylenimine) (PEI) is the standard benchmark amine material, it suffers from limited oxidative stability. Poly(propylenimine) (PPI), as an alternative, has previously demonstrated improved resistance to degradation under harsh oxidative conditions. Linear and branched PEI are commercially available, though at different molecular weights, while PPI is not commercially available. For this reason, a comparative study of all four polymers (linear PEI, branched PEI, linear PPI, branched PPI) has not been reported for DAC. In this study, we synthesize and compare low-molecular-weight (∼800 g/mol) linear (L) and branched (B) PEI and PPI supported on a model support, SBA-15 silica. These materials are evaluated for CO 2 adsorption under dry, DAC-relevant conditions (400 ppm of CO 2 , 30 °C). LPPI exhibited the highest amine efficiency at all loadings, reaching a maximum of 0.14 mmol CO 2 /mmol N, outperforming BPEI, while LPEI consistently showed the lowest uptake capacity. Temperature-programmed desorption reveals that the structure of the amine polymer impacts the CO 2 binding strength, with branched polymers displaying higher desorption energies of 102−111 kJ/mol. In situ infrared spectroscopy experiments show that all sorbents preferentially capture CO 2 as ammonium carbamate. Isobaric CO 2 uptake studies further underscore the influence of polymer mobility and support pore crowding on performance, while demonstrating the sorbents’ performance at elevated temperatures and CO 2 concentrations. All materials demonstrated good stability over 25 adsorption−desorption cycles using thermal regeneration in an inert gas purge, with only BPPI displaying a 10−11% decrease in capacity/amine efficiency during cycling, possibly due to the loss of low molecular weight, oligomeric amines. This is the first side-by-side comparison of the CO 2 sorption properties of linear and branched PEI and PPI with similar molecular weights. These findings highlight the significant role of polymer architecture in CO 2 capture efficiency and inform future designs of durable, high-performance DAC sorbents.

adsorbents↗
DOE OSTI2022

Predictive coarse-grained (CG) modeling of morphologies in polymer nanocomposites with specific and directional intermolecular interactions (Final Report)

The overarching goal of the proposed work was to develop predictive models for investigating structure and dynamics in soft materials with chemistries that have specific and directional molecular interactions. The motivation behind studying materials with specific and directional interactions lies in the many desirable features these interactions provide when designing novel soft materials. Soft materials with specific and direction interactions (such as hydrogen bonds or H-bonds) can have a) thermally reversible phase behavior with different functions with varying temperature, b) precisely tuned nanostructure with desirable geometries that afford unique physical properties (e.g., color response, mechanical properties) and c) well-mixed/blended morphologies that are useful for variety of applications in energy field (e.g., materials for batteries require use of blended polymers where one domain gives superior mechanical properties and one domain promotes electrical conduction). Notably, biology makes extensive use of specific and directional interactions, in many cases based on H-bonds, to construct materials with precisely defined architectures and properties. Engineered soft materials with precisely tuned nanostructures and improved processiblity through thermoresponsive phase behavior are useful in numerous applications that are relevant to the Department of Energy (DOE) including high efficiency electronic devices, light-weight high-strength composite materials for batteries and fuel cells, and polymer membranes for separations, etc. While past computational studies have been tremendously useful in understanding molecular phenomena and guiding synthesis of new macromolecular soft materials for a wide variety of applications, the inability to capture small scale specific and directional interactions alongside macromolecular length and time scales represented a key limitation of most studies to date. Our work in this project addressed this grand challenge in computational materials chemistry, i.e., ability to model the anisotropic, directional, and specific interactions that govern the behavior of many macromolecular soft matter systems of interest, thus, has greatly expanded the predictive potential of simulations. Specifically the key outcomes were: successful development of new coarse-grained (CG) polymer models to study generic and specific polymer chemistries in which hydrogen-bonding interactions are dominant. These CG models were then used in molecular simulations to study structure and thermodynamics in polymer nanocomposites and blends; some studies were conducted in collaboration with experimentalists. We also published a perspective and a viewpoint which included some of the work we completed in this DOE project; we believe these perspective and viewpoint articles guide other researchers in the soft materials community on how to extend the computational approaches and models we have developed for the purposes of their studies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of Carboxymethyl Cellulose as a Thickening Agent for Glauber’s Salt-Based Low Temperature PCM

This work is focused on a novel, promising low temperature phase change material (PCM), based on the eutectic Glauber’s salt composition. To allow phase transition within the refrigeration range of temperatures of +5 °C to +12 °C, combined with a high repeatability of melting–freezing processes, and minimized subcooling, the application of three variants of sodium carboxymethyl cellulose (Na-CMC) with distinct molecular weights (700,000, 250,000, and 90,000) is considered. The primary objective is to optimize the stabilization of this eutectic PCM formulation, while maintaining the desired enthalpy level. Preparation methods are refined to ensure repeatability in mixing components, thereby optimizing performance and stability. Additionally, the influence of Na-CMC molecular weight on stabilization is examined through differential scanning calorimetry (DSC), T-history, and rheology tests. The PCM formulation of interest builds upon prior research in which borax, ammonium chloride, and potassium chloride were used as additives to sodium sulfate decahydrate (Glauber’s salt), prioritizing environmentally responsible materials. The results reveal that CMC with molecular weights of 250 kg/mol and 90 kg/mol effectively stabilize the PCM without phase separation issues, slowing crystallization kinetics. Conversely, CMC of 700 kg/mol proved ineffective due to the disruption of gel formation at its low gel point, hindering higher concentrations. Calculations of ionic concentration indicate higher Na ion content in PCM stabilized with 90 kg/mol CMC, suggesting increased ionic interactions and gel strength. A tradeoff is discovered between the faster crystallization in lower molecular weight CMC and the higher concentration required, which increases the amount of inert material that does not participate in the phase transition. After thermal cycling, the best formulation had a latent heat of 130 J/g with no supercooling, demonstrating excellent performance. This work advances PCM’s reliability as a thermal energy storage solution for diverse applications and highlights the complex relationship between Na-CMC molecular weight and PCM stabilization.

25 ENERGY STORAGE↗
DOE OSTI2026

Co-templating of polyoxoniobates and silicate/germanate trimer-rings in crystals and inorganic gels

Polyoxometalate (POM) supramolecular gels are a growing family of materials, both for understanding fundamental self-assembly and fabricating flexible monolithic materials that retain the function of metal oxides. Here, we exploited the pH-dependent speciation of polyoxoniobates (PONbs), targeting the formation of PONb-containing supramolecular gels that contain other low molecular weight components (silicate, germanate, phosphate, and carbonate). The introduction of gaseous CO 2 into aqueous hexaniobate solutions resulted in the formation of both new crystalline phases and highly transparent gels. The crystalline phases, formulated Cs 24 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Si 3 O 9 )]·19.6H 2 O and Cs 21 Na 3 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Ge 3 O 9 )]·33.6H 2 O are templated by a rare planar [X 3 O 9 ] 6− (X = Si, Ge) ring. Crystalline phases were not obtained with phosphate; instead, the gels contain a mixture of phosphate-centred PONbs and network-forming phosphate. POM speciation within the gels, physical properties, and assembly mechanisms were benchmarked by solution and solid-state nuclear magnetic resonance (NMR) spectroscopy, vibrational spectroscopies, small-angle X-ray scattering (SAXS), and thermogravimetry-mass spectroscopy. Optical analysis and dielectric behavior of the gels confirmed that they are highly transparent ionic and electronic conductors. The alkali and hydroxide concentration controls the formation of crystalline materials or supramolecular gels while maintaining the same network building blocks, providing a rare opportunity to describe the molecular-level structure of inorganic amorphous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Autonomous continuous flow reactor synthesis for scalable atom-precision

With new instrumentation design, robotics, and in-operando hyphenated analytical tool automation, the intelligent discovery of synthesis pathways is becoming feasible. It can potentially bridge the gap for the scale-up of new materials. In this article, we review current progress and describe a new system that uses an autonomous continuous flow chemistry framework to translate high-quality lead molecules and materials to quantities that can meet scalability demands. At the core is a continuous flow synthesis platform that can design its viable synthesis pathway to a particular molecule or material and then autonomously carry it out. This is realized by integrating: (1) A workflow/architecture for multimode chemical/materials characterization in-line. The in-line characterization modes are NMR, ESR, IR, Raman, UV-Vis, GC-MS, and HPLC, along with ex-situ modes for X-Ray and neutron scattering; (2) Integration for feedback/analysis/data storage of the control variables; (3) A core software stack that includes deep learning and reinforcement learning alongside quantum chemistry and molecular dynamics; (4) On-demand compute architectures that parse calculations to compute resources needed which include light-weight edge, mid-level edge (NVIDA DGX-2), and high-performance computing. We demonstrate preliminary results on how this autonomous reactor system can enhance our ability to deliver deuterated materials, copolymers, and site-substituted molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗