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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Toward Spatial Control of Reaction Selectivity on Photocatalysts Using Area-Selective Atomic Layer Deposition on the Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost, green H 2 . However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO 2 films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO 2 was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO 2 -encapsulated Pt effectively suppressed undesired H 2 oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO 2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.

08 HYDROGEN↗
DOE OSTI2026

Nicotinamide-Loaded Peptoid Nanotubes for Energy Regeneration in Acute Brain Injury

Acute brain injuries such as perinatal asphyxia, stroke, and traumatic brain injury result in ischemia, oxidative stress, excitotoxicity, and inflammation, leading to a depletion of ATP. Nicotinamide adenine dinucleotide (NAD+) is crucial for ATP regeneration and DNA repair during postinjury recovery. However, the therapeutic benefits of NAD+ and its precursors, such as nicotinamide (NAM), are limited by challenges in achieving effective cell-specific intracellular delivery. In this study, we use a nanopeptoid delivery strategy to replenish the cellular redox state and increase energy production in the acutely injured brain. By self-assembling peptoids into tubular structures, we created biocompatible NAM-conjugated peptoid nanotubes (NAM-PNTs) that vary in tubular length. NAM-PNTs demonstrated significant therapeutic benefits by enhancing cell viability and replenishing intracellular ATP levels within 24 h of treatment in oxygen–glucose-deprived (OGD) BV-2 cells. In organotypic brain slices, NAM-PNT treatment promoted glial proliferation, reduced proinflammatory cytokines, and increased anti-inflammatory cytokines after OGD, an ex vivo model of hypoxia-ischemia. The effect of NAM-PNTs is associated with their uptake into microglia via fluid-phase phagocytosis and caveolae-mediated endocytosis. A single systemic dose of NAM-PNTs localized in microglia in the injured hemisphere and reduced brain tissue loss and improved neuropathology after hypoxia-ischemia in term-equivalent rats. These findings highlight the therapeutic potential of NAM-PNTs for cell-specific targeted delivery and energy restoration in the acutely injured neonatal brain. In the neonatal brain injury field, this work demonstrates the development of an innovative nanoparticle platform from first-principles design and synthesis to in vitro screening and then demonstration of efficacy in vivo .

ATP↗
DOE OSTI2026

Two-Dimensional Perovskite Single-Nanowire Photodetectors

High-performance microphotodetectors require materials that combine strong light–matter interaction, fast charge transport, and ambient stability. Here, we demonstrate single-nanowire devices based on the 2D perovskite (TPA3) 2 PbBr 4 , synthesized via a controlled slow-cooling self-assembly process that yields defect-minimized, anisotropic nanowires with smooth facets. These microphotodetectors exhibit ultralow dark currents (∼10 –15 A), high responsivity (up to 156 mA W –1 ), and exceptional specific detectivity (∼10 11 Jones) under near-UV (405 nm) illumination, with rise and fall times in the millisecond regime. The superior detectivity is primarily driven by the suppression of thermal noise through the material’s ultralow dark current, while the millisecond temporal response is governed by high-intensity trap-filling dynamics. The devices maintain stable operation over 4000 s of continuous on/off cycling and show remarkable ambient stability over weeks, attributed to dense crystal packing and robust organic cation layers. Furthermore, the influence of nanowire thickness on the charge collection efficiency is systematically elucidated through optical penetration depth analysis, highlighting design principles for optimizing low-dimensional perovskite photodetectors. This study introduces single 2D perovskite nanowires as a versatile platform for miniaturized, high-performance optoelectronic devices.

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

Nanoscale Spatial Distribution of Supported Nanoparticles Controls Activity and Stability in Powder Catalysts for CO Oxidation and Photocatalytic H 2 Evolution

Here we discuss, supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports. We quantify distributions on the nanoscale using image statistics and show that the type of nanospatial distribution determines not only the stability, but also the activity of heterogeneous catalysts. Widely investigated systems (Au–TiO 2 for CO oxidation thermocatalysis and Pd–TiO 2 for H 2 evolution photocatalysis) were used to showcase the universal importance of nanoparticle spatial organization. Spatially and temporally resolved microkinetic modeling revealed that nonuniformly distributed Au nanoparticles suffer from local depletion of surface oxygen, and therefore lower CO oxidation activity, as compared to uniformly distributed nanoparticles. Nanoparticle spatial distribution also determines the stability of Pd–TiO 2 photocatalysts, because nonuniformly distributed nanoparticles sinter while uniformly distributed nanoparticles do not. This work introduces new tools to evaluate and understand catalyst collective (ensemble) properties in powder catalysts, which thereby pave the way to more active and stable heterogeneous catalysts.

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

Thermodynamics and Mechanism of a Photocatalyzed Stereoselective [2 + 2] Cycloaddition on a CdSe Quantum Dot

Colloidal quantum dots (QDs) have shown promise over the last few decades for a range of applications including single photon emission, in vivo imaging and photocatalysis. Recent experiments demonstrated that QDs impart stereoselectivity to triplet excited-state [2+2] cycloaddition reactions of alkenes photocatalyzed by the QD through self-assembly of the reagent molecules on the QD surface, but these experiments did not reveal the precise geometries of surface-bound molecules or their interactions with surface atoms. Here, a theoretical mechanistic approach is used to study such interactions for [2+2] cycloadditions of 4-vinylbenzoic acid derivatives on CdSe QDs. Spin-polarized periodic density functional theory (DFT) and non-periodic DFT calculations are deployed to determine the origin of the selectivity for the syn diastereomer of the resultant tetrasubstituted cyclobutane product via atomistic modelling of the CdSe surface and substrates, and determination of the thermodynamic energies of reactions for each step, the intermolecular interactions between the substrates, and the triplet state reaction paths. The calculations indicate that reaction selectivity arises from preferred binding of pairs through intermolecular interactions of substrate molecules on the QD surface in a syn-precursor structure followed by dimerization after triplet excitation. Further, these mechanisms are generalizable to other metal-enriched QD surfaces that have a similar surface structure to CdSe, such as InSe or CdTe. Design principles for anti diastereomer derivatives are also discussed.

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

Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces

The creation of stable molecular monolayers on metallic surfaces is a fundamental challenge of surface chemistry. N-Heterocyclic carbenes (NHCs) were recently shown to form self-assembled monolayers that are significantly more stable than the traditional thiols on Au system. In this study, we theoretically and experimentally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly than NHCs to Au surfaces without altering the surface structure. We deposit bis(diisopropylamino)cyclopropenylidene (BAC) on Au(111) using the molecular adduct BAC–CO 2 as a precursor and determine the structure, geometry, and behavior of the surface-bound molecules through high-resolution X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Our experiments are supported by density functional theory calculations of the molecular binding energy of BAC on Au(111) and its electronic structure. Our work is the first demonstration of surface modification with a stable carbene other than NHC; more broadly, it drives further exploration of various carbenes on metal surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Harnessing Peptide Binding to Capture and Reclaim Phosphate

With rising consumer demands, society is tapping into wastewater as an innovative source to recycle depleting resources. Novel reclamation technologies have been recently explored for this purpose, including several that optimize natural biological processes for targeted reclamation. However, this emerging field has a noticeable dearth of synthetic material technologies that are programmed to capture, release, and recycle specified targets; and of the novel materials that do exist, synthetic platforms incorporating biologically inspired mechanisms are rare. We present here a prototype of a materials platform utilizing peptide amphiphiles that has been molecularly engineered to sequester, release, and reclaim phosphate through a stimuli-responsive pH trigger, exploiting a protein-inspired binding mechanism that is incorporated directly into the self-assembled material network. This material is able to harvest and controllably release phosphate for multiple cycles of reuse, and it is selective over nitrate and nitrite. We have determined by simulations that the binding conformation of the peptide becomes constrained in the dense micelle corona at high pH such that phosphate is expelled when it otherwise would be preferentially bound. However, at neutral pH, this dense structure conversely employs multichain binding to further stabilize phosphate when it would otherwise be unbound, opening opportunities for higher-order conformational binding design to be engineered into this controllably packed corona. With this work, we are pioneering a new platform to be readily altered to capture other valuable targets, presenting a new class of capture and release materials for recycling resources on the nanoscale.

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

Conjugated Metal–Organic Macrocycles: Synthesis, Characterization, and Electrical Conductivity

The dimensional reduction of solids into smaller fragments provides a route to achieve new physical properties and gain deeper insight into the extended parent structures. Here, we report the synthesis of CuTOTP-OR (TOTP n – = 2,3,6,7-tetraoxidotriphenylene), a family of copper-based macrocycles that resemble truncated fragments of the conductive 2D metal–organic framework Cu 3 (HHTP) 2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). The planar metal–organic macrocycles self-assemble into ordered nanotubes with internal diameters of ~2 nm and short interlayer distances of ~3.20 Å. Strong π–π stacking interactions between macrocycles facilitate out-of-plane charge transport, and pressed pellet conductivities as high as 2(1)×10 -3 S cm -1 are observed. Peripheral alkyl functionalization enhances solution processability and enables the fabrication of thin-film field-effect transistor devices. Ambipolar charge transport is observed, suggesting similar behavior may be operative in Cu 3 (HHTP) 2 . By coupling the attractive features of metal–organic frameworks with greater processability, these macrocycles enable facile device integration and a more nuanced understanding of out-of-plane charge transport in 2D conductive metal–organic frameworks.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Supramolecular meso -Trick: Ambidextrous Mirror Symmetry Breaking in a Liquid Crystalline Network with Tetragonal Symmetry

Bicontinuous and multicontinuous network phases are among nature's most complex structures in soft matter systems. Here, a chiral bicontinuous tetragonal phase is reported as a new stable liquid crystalline intermediate phase at the transition between two cubic phases, the achiral double gyroid and the chiral triple network cubic phase with an I 23 space group, both formed by dynamic networks of helices. The mirror symmetry of the double gyroid, representing a meso -structure of two enantiomorphic networks, is broken at the transition to this tetragonal phase by retaining uniform helicity only along one network while losing it along the other one. This leads to a conglomerate of enantiomorphic tetragonal space groups, P 4 1 2 1 2 and P 4 3 2 1 2. Phase structures and chirality were analyzed by small-angle X-ray scattering (SAXS), grazing-incidence small-angle X-ray scattering (GISAXS), resonant soft X-ray scattering (RSoXS) at the carbon K-edge, and model-dependent SAXS/RSoXS simulation. In conclusion, our findings not only lead to a new bicontinuous network-type three-dimensional mesophase but also reveal a mechanism of mirror symmetry breaking in soft matter by partial meso -structure racemization at the transition from enantiophilic to enantiophobic interhelical self-assembly.

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

Formation Mechanism of Flower-like Polyacrylonitrile Particles

Flower-like polyacrylonitrile (PAN) particles have shown promising performance for numerous applications, including sensors, catalysis, and energy storage. However, the detailed formation process of these unique structures during polymerization has not been investigated. Here, we elucidate the formation process of flower-like PAN particles through a series of in situ and ex situ experiments. We have the following key findings. First, lamellar petals within the flower-like particles were predominantly orthorhombic PAN crystals. Second, branching of the lamellae during the particle formation arose from PAN's fast nucleation and growth on pre-existing PAN crystals, which was driven by the poor solubility of PAN in the reaction solvent. Third, the particles were formed to maintain a constant center-to-center distance during the reaction. The separation distance was attributed to strong electrostatic repulsion, which resulted in the final particles' spherical shape and uniform size. Lastly, we employed the understanding of the formation mechanism to tune the PAN particles' morphology using several experimental parameters including incorporating comonomers, changing temperature, adding nucleation seeds, and adjusting the monomer concentration. Here these findings provide important insights into the bottom-up design of advanced nanostructured PAN-based materials and controlled polymer nanostructure self-assemblies.

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

A Solid Zn-Ion Conductor from an All-Zinc Metal–Organic Framework Replete with Mobile Zn 2+ Cations

Here, we describe the synthesis and properties of Zn 3 [(Zn 4 Cl) 3 (BTT) 8 ] 2 (ZnZnBTT, BTT 3– = 1,3,5-benzenetristetrazolate), a heretofore unknown member of a well-known, extensive family of metal–organic frameworks (MOFs) with the general formula M II 3 [(M II 4 Cl) 3 (BTT) 8 ] 2 , which adopts an anionic, sodalite-like structure. As with previous members in this family, ZnZnBTT presents two crystallographically distinct metal cations: a skeletal Zn 2+ site, fixed within Zn 4 Cl(tetrazole) 8 secondary building units (SBUs), and a charge-balancing Zn 2+ site. Self-assembly of ZnZnBTT from its building blocks has remained elusive; instead, we show that ZnZnBTT is readily accessed by quantitative postsynthetic exchange of all Mn 2+ ions in MnMnBTT with zinc. We further demonstrate that ZnZnBTT is a promising Zn-ion conductor owing to the mobile charge-balancing extra-framework Zn 2+ cations. The new material displays a Zn-ion conductivity of σ = 1.15 × 10 –4 S/cm at room temperature and a relatively low activation energy of E a = 0.317 eV, enabling potential applications in the emerging field of quasi-solid-state zinc-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Dynamic Nanocrystal Superlattices with Thermally Triggerable Lubricating Ligands

The size-dependent and collective physical properties of nanocrystals (NCs) and their self-assembled superlattices (SLs) enable the study of mesoscale phenomena and the design of metamaterials for a broad range of applications. However, the limited mobility of NC building blocks in dried NCSLs often hampers the potential for employing postdeposition methods to produce high-quality NCSLs. In this study, we present tailored promesogenic ligands that exhibit a lubricating property akin to thermotropic liquid crystals. The lubricating ability of ligands is thermally triggerable, allowing the dry solid NC aggregates deposited on the substrates with poor ordering to be transformed into NCSLs with high crystallinity and preferred orientations. The interplay between the dynamic behavior of NCSLs and the molecular structure of the ligands is elucidated through a comprehensive analysis of their lubricating efficacy using both experimental and simulation approaches. Coarse-grained molecular dynamic modeling suggests that a shielding layer from mesogens prevents the interdigitation of ligand tails, facilitating the sliding between outer shells and consequently enhancing the mobility of NC building blocks. Further, the dynamic organization of NCSLs can also be triggered with high spatial resolution by laser illumination. The principles, kinetics, and utility of lubricating ligands could be generalized to unlock stimuli-responsive metamaterials from NCSLs and contribute to the fabrication of NCSLs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Growth of Nanocrystal Superlattices from Liquid Crystals

The growth of superlattices (SLs) made from self-assembled nanocrystals (NCs) is a powerful method for creating new materials and gaining insight into fundamental molecular dynamics. Previous explorations of NCSL syntheses have mostly compared them to crystallization. However, NCSL synthesis has not broadly shown cooling crystallization from saturated solutions as a reversible crystallization–dissolution process. We demonstrate the reversible growth of NCSLs by dispersing NCs in liquid crystal (LC) “smart solvents,” and harnessing the transitions between the isotropic and nematic phases of the LCs. The growth mode and morphology can be tuned. Furthernore, this process is a model platform for studying crystallization and demonstrates great potential in manufacturing NCSLs as colloidal crystals through liquid-phase epitaxy or colloidal synthesis.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Interfacial Electrochemistry of Catalyst-Coordinated Graphene Nanoribbons

The immobilization of molecular electrocatalysts on conductive electrodes is an appealing strategy for enhancing their overall activity relative to those of analogous molecular compounds. Here, in this study, we report on the interfacial electrochemistry of self-assembled two-dimensional nanosheets of graphene nanoribbons (GNR-2DNS) and analogs containing a Rh-based hydrogen evolution reaction (HER) catalyst (RhGNR-2DNS) immobilized on conductive electrodes. Proton-coupled electron transfer (PCET) taking place at N-centers of the nanoribbons was utilized as an indirect reporter of the interfacial electric fields experienced by the monolayer nanosheet located within the electric double layer. The experimental Pourbaix diagrams were compared with a theoretical model, which derives the experimental Pourbaix slopes as a function of parameter f, a fraction of the interfacial potential drop experienced by the redox-active group. Interestingly, our study revealed that GNR-2DNS was strongly coupled to glassy carbon electrodes (f = 1), while RhGNR-2DNS was not (f = 0.15). We further investigated the HER mechanism by RhGNR-2DNS using electrochemical and X-ray absorption spectroelectrochemical methods and compared it to homogeneous molecular model compounds. RhGNR-2DNS was found to be an active HER electrocatalyst over a broader set of aqueous pH conditions than its molecular analogs. We find that the improved HER performance in the immobilized catalyst arises due to two factors. First, redox-active bipyrimidine-based ligands were shown to dramatically alter the activity of Rh sites by increasing the electron density at the active Rh center and providing RhGNR-2DNS with improved catalysis. Second, catalyst immobilization was found to prevent catalyst aggregation that was found to occur for the molecular analog in the basic pH. Overall, this study provides valuable insights into the mechanism by which catalyst immobilization can affect the overall electrocatalytic performance.

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

Functional Design of Peptide Materials Based on Supramolecular Cohesion

Peptide materials offer a broad platform to design biomimetic soft matter, and filamentous networks that emulate those in extracellular matrices and the cytoskeleton are among the important targets. Given the vast sequence space, a combination of computational approaches and readily accessible experimental techniques is required to design peptide materials efficiently. Here, we report here on a strategy that utilizes this combination to predict supramolecular cohesion within filaments of peptide amphiphiles, a property recently linked to supramolecular dynamics and consequently bioactivity. Using established coarse-grained simulations on 10,000 randomly generated peptide sequences, we identified 3500 likely to self-assemble in water into nanoscale filaments. Atomistic simulations of small clusters were used to further analyze this subset of sequences and identify mathematical descriptors that are predictive of intermolecular cohesion, which was the main purpose of this work. We arbitrarily selected a small cohort of these sequences for chemical synthesis and verified their fiber morphology. With further characterization, we were able to link the latent heat associated with fiber to micelle transitions, an indicator of cohesion and potential supramolecular dynamicity within the filaments, to calculated hydrogen bond densities in the simulation clusters. Based on validation from in situ synchrotron X-ray scattering and differential scanning calorimetry, we conclude that the phase transitions can be easily observed by very simple polarized light microscopy experiments. We are encouraged by the methodology explored here as a relatively low-cost and fast way to design potential functions of peptide materials.

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

Structural Heterogeneity and Hydrodynamics of an Intrinsically Disordered Protein Condensate

Biology demonstrates precise control over the free-energy landscape through the selective partitioning of biomacromolecules into membraneless organelles, enabling essential functions such as biochemical transformations, signaling cascades, and mechanical reinforcement. Although the function of these condensates depends on their underlying structure and hydrodynamics, molecular-scale information on these systems remains sparse. Here, in this study, neutron scattering is used to probe the organization and dynamics of the intrinsically disordered N-terminal domain of Galectin-3, an extracellular lectin responsible for facilitating liquid–liquid phase separation on the cellular surface, in both dilute and condensed phases. Dilute solutions contain isolated protein chains in equilibrium with mesoscopic clusters, whereas the condensed phase adopts a bicontinuous, microemulsion-like morphology. The dilute phase behavior is quantitatively described by coarse-grained polymer models from soft-matter physics, demonstrating their predictive power for complex biological proteins. At elevated concentrations, the proteins self-assemble akin to block copolymers, microphase separating through the aggregation of hydrophobic domains along the protein contour. The resulting condensate remains fluid-like despite a 25-fold increase in concentration; its internal hydrodynamics slow by only a factor of 3 relative to dilute protein chains. These results provide a molecular-level framework for how disordered proteins achieve both the structural complexity and dynamic fluidity of biomolecular condensates.

Carrick, Brian R. [Massachusetts Inst. of Technolo↗
DOE OSTI2020

Control of Molecular Bonding Strength on Metal Catalysts with Organic Monolayers for CO 2 Reduction

The development of separate levers for controlling the bonding strength of different reactive species on catalyst surfaces is challenging but essential for the design of highly active and selective catalysts. For example, during CO 2 reduction, production of CO often requires balancing a trade-off between the adsorption strength of the reactant and product states: weak binding of CO is desirable from a selectivity perspective, but weak binding of CO 2 leads to low activity. Here in this paper, we demonstrate a new method of controlling both CO 2 adsorption and CO desorption over supported metal catalysts by employing a single self-assembly step where organic monolayer films were deposited on the catalyst support. Binding of phosphonic acid monolayers on supported Pt and Pd catalysts weakened CO binding via a through-support effect. The weakened CO adsorption was generally accompanied by decreased adsorption and reactivity of CO 2 . However, by the incorporation of basic amine functions at controlled positions in the modifying film, strong CO 2 adsorption and hydrogenation reactivity could be restored. Thus, both through-surface and through-space interactions could be manipulated by design of the organic modifiers. After surface modification, the catalysts exhibited significantly improved selectivity (up to ~99% at conversions near 50%) and activity toward CO production. Moreover, the rate of deactivation was notably reduced due to prevention of CO poisoning.

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

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers

Poor ionic conductivity of the catalyst-binding, submicrometer- thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗