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At least 73 records · Page 4

A Heteromeric Carboxylic Acid Based Single-Crystalline Crosslinked Organic Framework

The development of large pore single-crystalline covalently linked organic frameworks is critical in revealing the detailed structure-property relationship with substrates. One emergent approach is to photo-crosslink hydrogen-bonded molecular crystals. Introducing complementary hydrogen-bonded carboxylic acid building blocks is promising to construct large pore networks, but these molecules often form interpenetrated networks or non-porous solids. In this report we introduced heteromeric carboxylic acid dimers to construct a non-interpenetrated molecular crystal. Crosslinking this crystal precursor with dithiols afforded a large pore single-crystalline hydrogen-bonded crosslinked organic framework H C OF-101. X-ray diffraction analysis revealed H C OF-101 as an interlayer connected hexagonal network, which possesses flexible linkages and large porous channels to host a hydrazone photoswitch. Multicycle Z/E-isomerization of the hydrazone took place reversibly within H C OF-101, showcasing the potential use of H C OF-101 for optical information storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relationship between A-site cation and magnetic structure in 3d–5d–4f double perovskite iridates Ln 2 NiIrO 6 ( Ln = La, Pr, Nd)

We report a comprehensive investigation of Ln 2 NiIrO 6 (Ln=La, Pr, Nd) using thermodynamic and transport properties, neutron powder diffraction, resonant inelastic x-ray scattering, and density-functional theory (DFT) calculations to investigate the role of A-site cations on the magnetic interactions in this family of hybrid 3d–5d–4f compositions. Magnetic structure determination using neutron diffraction reveals antiferromagnetism for La 2 NiIrO 6 , a collinear ferrimagnetic Ni and Ir state that is driven to long-range antiferromagnetism upon the onset of Nd ordering in Nd 2 NiIrO 6 , and a noncollinear ferrimagnetic Ni and Ir sublattice interpenetrated by a ferromagnetic Pr lattice for Pr 2 NiIrO 6 . For Pr 2 NiIrO 6 , heat-capacity results reveal the presence of two independent magnetic sublattices, and transport resistivity indicates insulating behavior and a conduction pathway that is thermally mediated. Here, a first principles DFT calculation elucidates the existence of the two independent magnetic sublattices within Pr 2 NiIrO 6 and offers insight into the behavior in La 2 NiIrO 6 and Nd 2 NiIrO 6 . Resonant inelastic x-ray scattering is consistent with spin-orbit coupling splitting the t 2 g manifold of octahedral Ir 4+ into a J eff = 1/2 and J eff = 3/2 state for all members of the series considered.

36 MATERIALS SCIENCE↗

Pyrochlore-type lanthanide titanates and zirconates: Synthesis, structural peculiarities, and properties

This contribution provides a thorough examination of the structural characteristics of pyrochlore-type lanthanide titanates and zirconates Ln2Ti2O7 and Ln2Zr2O7, across various length scales. This paper also examines their processing, interesting physical properties (electrical, magnetic, and thermal characteristics), and responses to high pressure and ion irradiation. Brief sections on the elemental oxides' crystal chemistry, pertinent phase diagrams, and energetics of defect formation are also provided. Pyrochlore-type Ln2Ti2O7 and Ln2Zr2O7 stand out as truly multifunctional materials. Moreover, they have emerged as fascinating materials due to magnetic geometrical frustration, arising from the ordering of magnetic Ln3+ and non-magnetic Ti4+ (or Zr4+) cations into separate, interpenetrating lattices of corner-sharing tetrahedra. This results in a diverse array of exotic magnetic ground states, such as spin-ice (e.g., Dy2Ti2O7 or Ho2Ti2O7) or quantum spin ice (e.g., Tb2Ti2O7), observed at both low and room temperatures. They also exhibit varied electrical and electrochemical characteristics. Some members such as Gd2Zr2O7, function as fast ion conductors with a conductivity (σ) of ≈10−2 S·cm−1 at 800 °C and activation energy (Ea) ranging from 0.85 to 1.52 eV, depending on the degree of structural disorder. Others, such as Gd2TiMoO7, are mixed ionic-electronic conductors with σ ≈ 25 S·cm−1 at 1000 °C, making them promising candidate materials for applications in energy conversion and storage devices and oxygen separation membranes. Their exceptionally low thermal conductivity (e.g., κ ∼ 1.1–1.7 W·m−1·K−1 between 700 and 1200 °C for Ln2Zr2O7), close to the glass-like lower limit of highly disordered solids, positions them as valuable materials for thermal barrier coatings. They can also effectively accommodate actinides (e.g., Pu, Np, Cm, Am) in solid solutions and sustain prolonged exposure to radiation due to alpha-decay events, while preserving the integrity of the periodic atomic structure. Proposed as major components in actinide-bearing ceramics, they contribute to the long-term immobilization and disposal of long-lived waste radionuclides from nuclear programs. Some of these properties are displayed simultaneously, opening avenues for new applications. Despite the wealth of data available in the literature, this review highlights the need for a better understanding of order/disorder processes in pyrochlore-type materials and the influence of the structural length scale on their physical and chemical properties. Recent experimental evidence has revealed that pyrochlore short-range structure is far more complex than originally thought. Moreover, pyrochlore local structure is now believed to include short-range, lower symmetry, ordered domains, such as the orthorhombic weberite-type of structure. Notably, short- and long-range structures appear decoupled across different length scales and temperature regimes, and these differences persist even in well-ordered samples. We believe that the pyrochlore structure offers a unique opportunity for examining the interplay between chemical composition, defect chemistry, and properties. In Memoriam: Rodney C. Ewing, Fondly Remembered.

Physics↗

Transport–Friendly Microstructure in SSC–MEA: Unveiling the SSC Ionomer–Based Membrane Electrode Assemblies for Enhanced Fuel Cell Performance

The significant role of the cathodic binder in modulating mass transport within the catalyst layer (CL) of fuel cells is essential for optimizing cell performance. This investigation focuses on enhancing the membrane electrode assembly (MEA) through the utilization of a short-side-chain perfluoro-sulfonic acid (SSC-PFSA) ionomer as the cathode binder, referred to as SSC-MEA. This study meticulously visualizes the distinctive interpenetrating networks of ionomers and catalysts, and explicitly clarifies the triple-phase interface, unveiling the transport-friendly microstructure and transport mechanisms inherent in SSC-MEA. The SSC-MEA exhibits advantageous microstructural features, including a better-connected ionomer network and well-organized hierarchical porous structure, culminating in superior mass transfer properties. Relative to the MEA bonded by long-side-chain perfluoro-sulfonic acid (LSC-PFSA) ionomer, noted as LSC-MEA, SSC-MEA exhibits a notable peak power density (1.23 W cm –2 ), efficient O 2 transport, and remarkable proton conductivity (65% improvement) at 65 °C and 70% relativity humidity (RH). These findings establish crucial insights into the intricate morphology-transport-performance relationship in the CL, thereby providing strategic guidance for developing highly efficient MEA.

25 ENERGY STORAGE↗

Modulation of CO 2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker

Metal–organic frameworks (MOFs) have attracted significant attention as sorbents due to their high surface area, tunable pore volume and pore size, coordinatively unsaturated metal sites, and ability to install desired functional groups by post-synthetic modification. Herein, we report three new MOFs with pillar–paddlewheel structures that have been synthesized solvothermally from the mixture of the carboxylate–pyrazole flexible linker (H 2 L), 4,4-bipyridine (BPY)/triethylenediamine (DABCO), and Zn(II)/Cu(II) ions. The MOFs obtained, namely [Zn II (L)BPY], [Cu II (L)BPY], and [Cu II (L)DABCO], exhibit two-fold interpenetration and dinuclear paddle–wheel nodes. The Zn(II)/Cu(II) cations are coordinated by two equatorial L linkers that result in two-dimensional sheets which in turn are pillared by BPY or DABCO in the perpendicular direction to obtain a neutral three-dimensional framework that shows one-dimensional square channels. The three pillar-layered MOFs were characterized as microporous materials showing high crystalline stability after activation at 120 °C and CO 2 adsorption. All MOFs contain uncoordinated Lewis basic pyrazole nitrogen atoms in the framework which have an affinity toward CO 2 and hence could potentially serve as CO 2 adsorption material. The CO 2 uptake capacity was initially enhanced by replacing Zn with Cu and then replacing the pillar, going from BPY to DABCO. Overall, all the MOFs exhibit low isosteric heat (Q st ) of adsorption which signifies an advantage due to the energy required for the adsorption and regeneration processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Optimized Fibril Network Morphology Enables High‐Efficiency and Ambient‐Stable Polymer Solar Cells

Abstract Morphological stability is crucially important for the long‐term stability of polymer solar cells (PSCs). Many high‐efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene‐4,8‐dione (T1‐Cl) via a random copolymerization approach. It is found that all the copolymers can self‐assemble into a fibril nanostructure in films. By altering the T1‐Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT‐4F, O‐INIC3, EH‐INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high‐efficiency and ambient‐stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermally driven phase transitions in freestanding low-buckled silicene, germanene, and stanene

Low-buckled silicene, germanene, and stanene are group-IV graphene allotropes. They form a honeycomb lattice out of two interpenetrating (A and B) triangular sublattices that are vertically separated by a small distance Δ z . The atomic numbers Z of silicon, germanium, and tin are larger than that of carbon (Z C = 6), making them the first experimentally viable two-dimensional topological insulators. Those materials have a twice-energy-degenerate atomistic structure characterized by the buckling direction of the B sublattice with respect to the A sublattice [whereby the B atom either protrudes above (Δ z > 0) or below (Δ z < 0) the A atoms], and the consequences of that energy degeneracy on their elastic and electronic properties have not been reported thus far. Here, we uncover ferroelastic, bistable behavior on silicene, which turns into an average planar structure at about 600 K. Furthermore, the creation of electron and hole puddles obfuscates the zero-temperature spin-orbit coupling (SOC)-induced band gaps at temperatures as low as 200 K, which may discard silicene as a viable two-dimensional topological insulator for room-temperature applications. Germanene, on the other hand, never undergoes a low-buckled-to-planar two-dimensional transformation, becoming amorphous at around 675 K instead, and preserving its SOC-induced band gap despite band broadening. Stanene undergoes a transition onto a crystalline three-dimensional structure at about 300 K, preserving its SOC-induced electronic band gap up to that temperature. Unlike what is observed in silicene and germanene, stanene readily develops a higher-coordinated structure with a high degree of structural order. Furthermore, the structural phenomena are shown to have far-reaching consequences for the electronic and vibrational properties of those two-dimensional topological insulators.

36 MATERIALS SCIENCE↗

Reticular Structural Diversification of Zirconium Metal–Organic Frameworks Through Angular Ligand Configuration Control

Reticular chemistry offers practical guidelines for enlarging and enriching the arsenal of metal–organic frameworks (MOFs). However, reticular expansion to access mesoporous structures remains challenging due to limitations in achieving precise control over both the size and configuration during building units’ extension. Herein, we combine ligand isomerization and functionalization strategies to regulate the ligand configuration by systematically replacing aryl C–H groups with N atoms, resulting in angular dicarboxylate ligands with various symmetries. The assembly between a 4,4′-(pyridine-2,6-diyl)dibenzoic acid ligand (1N, C 2 symmetry) and 12-connected Zr 6 cluster leads to the formation of a pseudo ftw topology framework (NU-2611), where one pair of nose-to-nose 1N ligands resembles a tetra-topic ligand. When a 6,6′-(1,3-phenylene)dinicotinic acid ligand (2N, C S symmetry) was used, another pseudo ftw network NU-2612 was obtained with a 2-fold framework interpenetration. Interestingly, the planar [2,2′:6′,2″-terpyridine]-5,5″-dicarboxylic acid ligand (3N, C 2V symmetry) yielded an intriguing mesoporous Zr-MOF with kag topology. NU-2613 represents the first example of kag Zr-MOF designed to include large, well-defined mesopores. The diversity of these MOFs was further enhanced through post-synthetic metalation of linkers. Particularly, metalation of the chelating 3N ligand with Fe 3+ in NU-2613 enables efficient catalytic transformation within the functionalized channels. This work contributes insight into the reticular expansion of Zr-MOFs by finely-tuning the ligand planarity, advancing the structure diversification of mesoporous frameworks for specific applications.

Cluster chemistry↗

Tethering Effects in Oligomer-Based Metal–Organic Frameworks

Metal–organic frameworks (MOFs) can be con- structed using conventional molecular linkers or polymeric linkers (polyMOFs), but the relationship and relative properties of these related materials remain understudied. As an intermediate between these two extremes, a library of oligomeric ligand precursors (dimers, trimers) was used to prepare a series of oligomeric-linker MOFs (oligoMOFs) based on the prototypical IRMOF-1 system. IRMOF-1 was found to be remarkably tolerant to a wide variety of oligomeric linkers, the use of which greatly enhanced the MOF yield and prevented framework interpenetration. Tether length-dependent ordering of ligand and metal cluster orientations was also observed in these oligoMOFs. Improved low-humidity stability was found in oligoIRMOF-1 samples, with surface area preservation varying as a function of tether length and a complete suppression of crystalline hydrolysis products for all oligoIRMOF-1 materials. Furthermore, these findings pave the way toward a better understanding of the structure–function relationships between monomeric, oligomeric, and polymeric MOFs and highlight an underutilized strategy for tuning MOF properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D printed Mg-NiTi interpenetrating-phase composites with high strength, damping capacity, and energy absorption efficiency

It is of significance, but still remains a key challenge, to simultaneously enhance the strength and damping capacities in metals, as these two properties are often mutually exclusive. Here, we provide a multidesign strategy for defeating such a conflict by developing a Mg-NiTi composite with a bicontinuous interpenetrating-phase architecture through infiltration of magnesium melt into three-dimensionally printed Nitinol scaffold. The composite exhibits a unique combination of mechanical properties with improved strengths at ambient to elevated temperatures, remarkable damage tolerance, good damping capacities at differing amplitudes, and exceptional energy absorption efficiency, which is unprecedented for magnesium materials. The shape and strength after deformation can even be largely recovered by heat treatment. This study offers a new perspective for the structural and biomedical applications of magnesium.

36 MATERIALS SCIENCE↗

Polymerized small molecular acceptor based all-polymer solar cells with an efficiency of 16.16% via tuning polymer blend morphology by molecular design

All-polymer solar cells (all-PSCs) based on polymerized small molecular acceptors (PSMAs) have made significant progress recently. Here, we synthesize two A-DA’D-A small molecule acceptor based PSMAs of PS-Se with benzo[c][1,2,5]thiadiazole A’-core and PN-Se with benzotriazole A’-core, for the studies of the effect of molecular structure on the photovoltaic performance of the PSMAs. The two PSMAs possess broad absorption with PN-Se showing more red-shifted absorption than PS-Se and suitable electronic energy levels for the application as polymer acceptors in the all-PSCs with PBDB-T as polymer donor. Cryogenic transmission electron microscopy visualizes the aggregation behavior of the PBDB-T donor and the PSMA in their solutions. In addition, a bicontinuous-interpenetrating network in the PBDB-T:PN-Se blend film with aggregation size of 10~20 nm is clearly observed by the photoinduced force microscopy. The desirable morphology of the PBDB-T:PN-Se active layer leads its all-PSC showing higher power conversion efficiency of 16.16%.

14 SOLAR ENERGY↗

Coupled Experimental/Computational Investigation of the Dynamics of Interacting Magnetized Plasmas

The interaction, or interpenetration, of magnetized plasmas of different density and/or pressure occurs in a wide variety of natural and man-made systems. Such systems include extragalactic jets propagating into the intergalactic medium, solar coronal mass ejections into background solar wind, compact toroid (CT) fueling of magnetic fusion plasmas, and jets of capsule shell impurities into DT fusion fuel, which can lead to enhanced impurity mix in inertial fusion implosions. These plasmas may take the form of jets, with open, helical magnetic structure, or plasma “bubbles” with closed magnetic fields (B-fields), such as spheromaks or CT’s. Such structures, both open and closed B-field cases, can transport heat, particles and magnetic flux or magnetic helicity into background plasma regions. For example, the origin of extragalactic magnetic fields may be due, at least in part, to transport by astrophysical jets. The goal of this proposed work was to elucidate the detailed plasma and magnetic field dynamics of high-density plasma jets (open B-field) and bubbles (closed B-field) propagating into lower density background magnetized plasma through controlled laboratory experiments and closely coupled nonlinear MHD modeling. These experiments were conducted in the HelCat (Helicon-Cathode) linear plasma device at the University of New Mexico (UNM). Plasma jets and bubbles were launched via an existing compact coaxial plasma gun, mounted on the HelCat device. This gun produced plasmas tens of cm in scale and lasting tens of microseconds, thereby allowing detailed multipoint, space- and time-resolved measurements to be made routinely. The experiments were directly modeled using the extended magnetohydrodynamic (XMHD) PERSEUS code, developed at Cornell University [23,24]. Both experimental and numerical modeling work are ongoing. The main results to date are reported here. Additional supplemental funding for one year (8/1/2019 – 7/31/2020) supported numerical investigation of photoionization processes important in many low temperature plasmas, including the HelCat device. Initial results of this modeling work is also reported.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Transient Catenation in a Zirconium-Based Metal–Organic Framework and Its Effect on Mechanical Stability and Sorption Properties

Interpenetration of two or more sublattices is common among many metal–organic frameworks (MOFs). In this study, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery of spontaneous de-interpenetration through charged point-point repulsions

Entanglement is an energetically favorable occurrence, pervasive in both nature and synthetic systems, where networks prefer to entwine with one another rather than remain open and accessible. As a result of entanglement, valuable internal pore space, useful for applications such as catalysis, storage, and sensing, is lost. Here, we detail our discovery of a phenomenon termed “charged point-point repulsion,” which energetically favors dis-entanglement, transforming a densely packed uranium-based framework with 14.2 and 19.8 Å pores into an open material with 40.7 Å pores and record-high void fraction and pore volume. We anticipate that the phenomenon described in this work could be widely generalized for the direct and systematic production of non-entangled structures with an abundance of valuable pore space and far-reaching practical importance. More fundamentally, this study compels a re-evaluation of the thermodynamics of porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mesocrystalline Ordering and Phase Transformation of Iron Oxide Biominerals in the Ultrahard Teeth of Cryptochiton stelleri

Biological organisms naturally synthesize complex, hierarchical, multifunctional materials through mineralization processes at ambient conditions and under physiological pH. One such example is the ultrahard and wear-resistant radular teeth found in mollusks, which are used to scape against the rock to feed on algae. Herein, the biologically controlled structural development of the hard, outer magnetite-containing shell of the chitin teeth is revealed. Specifically, the formation of a series of mesocrystalline iron oxide phases, templated by chitin-binding proteins, is identified. The initial domains, consisting of ferrihydrite mesocrystals with a spherulite-like morphology, undergo a solid-state phase transformation to form magnetite while maintaining mesocrystallinity, likely via a shear-induced solid-state reaction, without any noticeable architectural changes. Subsequent growth via Ostwald ripening leads to nearly single-crystalline rod-like elements. In addition, an interpenetrating organic matrix is identified that, at early stages of tooth development, potentially contains iron-binding proteins that guide the self-assembly of the mesocrystalline mineral and influence the preferred orientation of the later-formed magnetite nanorods, which ultimately determines the mechanical behavior of the mature chiton teeth.

36 MATERIALS SCIENCE↗

Core-shell structured tow-pregs enabled additive manufacturing of continuously reinforced thermoset composites

One of the major challenges in thermally curable polymer composite additive manufacturing is the slow curing time of thermally curable resins, coupled with a significant drop in thermoset viscosity upon heating, making the formation of complex shapes difficult. To tackle these issues, we have introduced a novel rapid composite preformation strategy called Tow-Preg Cladding (TPC). This technique involves the use of a thin and rapidly curable dual-cure resin, which combines a thermally curable resin (such as epoxy) with a fast photo-curable resin. The dual-cure resin is applied as a coating over a thermally curable resin tow-preg, enabling the formation of a rigid cladding that supports and shapes the tow-pregs into the desired geometries and patterns. The key advantage of this approach lies in the sequential formation of an interpenetrating polymer network (IPN) at the interlayer between laminates, resulting from the curing of the photocurable resin and the thermally curable resin sequentially. This IPN formation enhances interlaminar bonding in the composite, contributing to its overall strength and performance. The composites produced using this technique exhibited impressive mechanical properties, including longitudinal tensile strength of 1058.2 MPa, longitudinal tensile modulus of 74.2 GPa, flexural strength of 1080.4 MPa, and flexural modulus of 41.7 GPa. Overall, our Tow-Preg Cladding approach shows great promise in overcoming the challenges associated with thermally curable polymer composite additive manufacturing. It offers a viable solution to creating strong, shape-specific thermoset composites efficiently with enhanced mechanical properties.

42 ENGINEERING↗

Multimode Metastructures: Novel Hybrid 3D Lattice Topologies

With the rapid proliferation of additive manufacturing and 3D printing technologies, architected cellular solids including truss-like 3D lattice topologies offer the opportunity to program the effective material response through topological design at the mesoscale. The present report summarizes several of the key findings from a 3-year Laboratory Directed Research and Development Program. The program set out to explore novel lattice topologies that can be designed to control, redirect, or dissipate energy from one or multiple insult environments relevant to Sandia missions, including crush, shock/impact, vibration, thermal, etc. In the first 4 sections, we document four novel lattice topologies stemming from this study: coulombic lattices, multi-morphology lattices, interpenetrating lattices, and pore-modified gyroid cellular solids, each with unique properties that had not been achieved by existing cellular/lattice metamaterials. The fifth section explores how unintentional lattice imperfections stemming from the manufacturing process, primarily sur face roughness in the case of laser powder bed fusion, serve to cause stochastic response but that in some cases such as elastic response the stochastic behavior is homogenized through the adoption of lattices. In the sixth section we explore a novel neural network screening process that allows such stocastic variability to be predicted. In the last three sections, we explore considerations of computational design of lattices. Specifically, in section 7 using a novel generative optimization scheme to design novel pareto-optimal lattices for multi-objective environments. In section 8, we use computational design to optimize a metallic lattice structure to absorb impact energy for a 1000 ft/s impact. And in section 9, we develop a modified micromorphic continuum model to solve wave propagation problems in lattices efficiently.

36 MATERIALS SCIENCE↗