A Low-Swelling Polymeric Mixed Conductor Operating in Aqueous Electrolytes
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99 GENERAL AND MISCELLANEOUS↗
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Results for “tailoring”
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Poly(vinyl alcohol) Hydrogels with Broad-Range Tunable Mechanical Properties via the Hofmeister Effect
Hydrogels, exhibiting wide applications in soft robotics, tissue engineering, implantable electronics, etc., often require sophisticately tailoring of the hydrogel mechanical properties to meet specific demands. For examples, soft robotics necessitates tough hydrogels; stem cell culturing demands various tissue-matching modulus; and neuron probes desire dynamically tunable modulus. Herein, a strategy to broadly alter the mechanical properties of hydrogels reversibly via tuning the aggregation states of the polymer chains by ions based on the Hofmeister effect is reported. An ultratough poly(vinyl alcohol) (PVA) hydrogel as an exemplary material (toughness 150 ± 20 MJ m -3 ), which surpasses synthetic polymers like poly(dimethylsiloxane), synthetic rubber, and natural spider silk is fabricated. With various ions, the hydrogel's various mechanical properties are continuously and reversibly in situ modulated over a large window: tensile strength from 50 ± 9 kPa to 15 ± 1 MPa, toughness from 0.0167 ± 0.003 to 150 ± 20 MJ m -3 , elongation from 300 ± 100% to 2100 ± 300%, and modulus from 24 ± 2 to 2500 ± 140 kPa. Importantly, the ions serve as gelation triggers and property modulators only, not necessarily required to remain in the gel, maintaining the high biocompatibility of PVA without excess ions. Overall, this strategy, enabling high mechanical performance and broad dynamic tunability, presents a universal platform for broad applications from biomedicine to wearable electronics.
36 MATERIALS SCIENCE↗
Tunable Stochasticity in an Artificial Spin Network
Metamaterials present the possibility of artificially generating advanced functionalities through engineering of their internal structure. Artificial spin networks, in which a large number of nanoscale magnetic elements are coupled together, are promising metamaterial candidates that enable the control of collective magnetic behavior through tuning of the local interaction between elements. In this work, the motion of magnetic domain-walls in an artificial spin network leads to a tunable stochastic response of the metamaterial, which can be tailored through an external magnetic field and local lattice modifications. This type of tunable stochastic network produces a controllable random response exploiting intrinsic stochasticity within magnetic domain-wall motion at the nanoscale. An iconic demonstration used to illustrate the control of randomness is the Galton board. In this system, multiple balls fall into an array of pegs to generate a bell-shaped curve that can be modified via the array spacing or the tilt of the board. A nanoscale recreation of this experiment using an artificial spin network is employed to demonstrate tunable stochasticity. Furthermore, this type of tunable stochastic network opens new paths toward post-Von Neumann computing architectures such as Bayesian sensing or random neural networks, in which stochasticity is harnessed to efficiently perform complex computational tasks.
Artificial spin network↗
Highly Efficient Pure‐Blue Light‐Emitting Diodes Based on Rubidium and Chlorine Alloyed Metal Halide Perovskite
Abstract Perovskite light‐emitting diodes (PeLEDs) are promising candidates for display and solid‐state lighting, due to their tunable colors, high conversion efficiencies, and low cost. However, the performance of blue PeLEDs is far inferior to that of the near‐infrared, red, and green counterparts. Here, the fabrication of pure‐blue PeLEDs with an emission peak at 475 nm, a peak external quantum efficiency of 10.1%, and a maximum luminance of 14 000 cd m −2 is demonstrated by tailoring the compositions of perovskites. The pure‐blue electroluminescence is achieved by simultaneous addition of rubidium and chlorine ions into CsPbBr 3 and incorporation of phenylethylammonium chloride forms quasi‐2D hybrid perovskites. The combination of these composition engineering results in blueshifted emissions without reducing the quantum yield. The judicious alloying is shown to be critical to result in the better morphology with suppressed current leakage and enhanced light outcoupling.
Yang, Yang↗
Selective Antisite Defect Formation in WS 2 Monolayers via Reactive Growth on Dilute W-Au Alloy Substrates
Defects are ubiquitous in 2D materials and can affect the structure and properties of the materials and also introduce new functionalities. Methods to adjust the structure and density of defects during bottom-up synthesis are required to control the growth of 2D materials with tailored optical and electronic properties. In this study, the authors present an Au-assisted chemical vapor deposition approach to selectively form S W and S2 W antisite defects, whereby one or two sulfur atoms substitute for a tungsten atom in WS 2 monolayers. Guided by first-principles calculations, they describe a new method that can maintain tungsten-poor growth conditions relative to sulfur via the low solubility of W atoms in a gold/W alloy, thereby significantly reducing the formation energy of the antisite defects during the growth of WS 2 . The atomic structure and composition of the antisite defects are unambiguously identified by Z-contrast scanning transmission electron microscopy and electron energy-loss spectroscopy, and their total concentration is statistically determined, with levels up to ≈5.0%. Furthermore, scanning tunneling microscopy/spectroscopy measurements and first-principles calculations also verified these antisite defects and revealed the localized defect states in the bandgap of WS 2 monolayers. This bottom-up synthesis method to form antisite defects should apply in the synthesis of other 2D materials.
2D materials↗
Graphitic Aza-Fused π-Conjugated Networks: Construction, Engineering, and Task-Specific Applications
2D π-conjugated networks linked by aza-fused units represent a pivotal category of graphitic materials with stacked nanosheet architectures. Extensive efforts have been directed at their fabrication and application since the discovery of covalent triazine frameworks (CTFs). Besides the triazine cores, tricycloquinazoline and hexaazatriphenylene linkages are further introduced to tailor the structures and properties. Diverse related materials have been developed rapidly, and a thorough outlook is necessitated to unveil the structure–property–application relationships across multiple subcategories, which is pivotal to guide the design and fabrication toward enhanced task-specific performance. Herein, the structure types and development of related materials including CTFs, covalent quinazoline networks, and hexaazatriphenylene networks, are introduced. Advanced synthetic strategies coupled with characterization techniques provide powerful tools to engineer the properties and tune the associated behaviors in corresponding applications. Case studies in the areas of gas adsorption, membrane-based separation, thermo-/electro-/photocatalysis, and energy storage are then addressed, focusing on the correlation between structure/property engineering and optimization of the corresponding performance, particularly the preferred features and strategies in each specific field. In the last section, the underlying challenges and opportunities in construction and application of this emerging and promising material category are discussed.
36 MATERIALS SCIENCE↗
Atomically Thin, Ionic–Covalent Organic Nanosheets for Stable, High–Performance Carbon Dioxide Electroreduction
The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO 2 reduction reaction (CO 2 RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic–covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO 2 -to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO 2 RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm –2 with CO Faradaic efficiency of >95% at –0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. Finally, this work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability.
36 MATERIALS SCIENCE↗
Quenching-Induced Defects Liberate the Latent Reversible Capacity of Lithium Titanate Anode
Interest in defect engineering for lithium-ion battery (LIB) materials is sparked by its ability to tailor electrical conductivity and introduce extra active sites for electrochemical reactions. However, harvesting excessive intrinsic defects in the bulk of the electrodes rather than near their surface remains a long-standing challenge. Here, a versatile strategy of quenching is demonstrated, which is exercised in lithium titanate (Li 4 Ti 5 O 12 , LTO), a renowned anode for LIBs, to achieve off-stoichiometry in the interior region. In situ synchrotron analysis and atomic-resolution microscopy reveal the enriched oxygen vacancies and cation redistribution after ice-water quenching, which can facilitate the native unextractable Li ions to participate in reversible cycling. Further, the fabricated LTO anode delivers a sustained capacity of 202 mAh g -1 in the 1.0–2.5 V range with excellent rate capability and overcomes the poor cycling stability seen in conventional defective electrodes. The feasibility of tuning the degree of structural defectiveness via quenching agents is also proven, which can open up an intriguing avenue of research to harness the intrinsic defects for improving the energy density of rechargeable batteries.
25 ENERGY STORAGE↗
Iridescence from Total Internal Reflection at 3D Microscale Interfaces: Mechanistic Insights and Spectral Analysis
An experimental investigation and the optical modeling of the structural coloration produced from total internal reflection interference within 3D microstructures are described. Ray-tracing simulations coupled with color visualization and spectral analysis techniques are used to model, examine, and rationalize the iridescence generated for a range of microgeometries, including hemicylinders and truncated hemispheres, under varying illumination conditions. An approach to deconstruct the observed iridescence and complex far-field spectral features into its elementary components and systematically link them to ray trajectories that emanate from the illuminated microstructures is demonstrated. The results are compared with experiments, wherein microstructures are fabricated with methods such as chemical etching, multiphoton lithography, and grayscale lithography. Microstructure arrays patterned on surfaces with varying orientation and size lead to unique color-traveling optical effects and highlight opportunities for how total internal reflection interference can be used to create customizable reflective iridescence. The findings herein provide a robust conceptual framework for rationalizing this multibounce interference mechanism and establish approaches for characterizing and tailoring the optical and iridescent properties of microstructured surfaces.
36 MATERIALS SCIENCE↗
Molybdenum Disulfide Nanoribbons with Enhanced Edge Nonlinear Response and Photoresponsivity
MoS 2 nanoribbons have attracted increased interest due to their properties, which can be tailored by tuning their dimensions. Herein, the growth of MoS 2 nanoribbons and triangular crystals formed by the reaction between films of MoOx (2 2 nanoribbons arising from distinct contributions from the single–layer edges and multilayer core. Nanoscale imaging reveals a blue-shifted exciton emission of the monolayer edge compared to the isolated MoS 2 monolayers due to built-in local strain and disorder. We further report on an ultrasensitive photodetector made of a single MoS 2 nanoribbon with a responsivity of 8.72 × 10 2 A W –1 at 532 nm, among the highest reported up-to-date for single-nanoribbon photodetectors. These findings can inspire the design of MoS 2 semiconductors with tunable geometries for efficient optoelectronic devices.
36 MATERIALS SCIENCE↗
Aerosol‐Jet‐Printable Covalent Organic Framework Colloidal Inks and Temperature‐Sensitive Nanocomposite Films
Abstract With molecularly well‐defined and tailorable 2D structures, covalent organic frameworks (COFs) have emerged as leading material candidates for chemical sensing, storage, separation, and catalysis. In these contexts, the ability to directly and deterministically print COFs into arbitrary geometries will enable rapid optimization and deployment. However, previous attempts to print COFs have been restricted by low spatial resolution and/or post‐deposition polymerization that limits the range of compatible COFs. Here, these limitations are overcome with a pre‐synthesized, solution‐processable colloidal ink that enables aerosol jet printing of COFs with micron‐scale resolution. The ink formulation utilizes the low‐volatility solvent benzonitrile, which is critical to obtaining homogeneous printed COF film morphologies. This ink formulation is also compatible with other colloidal nanomaterials, thus facilitating the integration of COFs into printable nanocomposite films. As a proof‐of‐concept, boronate‐ester COFs are integrated with carbon nanotubes (CNTs) to form printable COF‐CNT nanocomposite films, in which the CNTs enhance charge transport and temperature sensing performance, ultimately resulting in high‐sensitivity temperature sensors that show electrical conductivity variation by 4 orders of magnitude between room temperature and 300 °C. Overall, this work establishes a flexible platform for COF additive manufacturing that will accelerate the incorporation of COFs into technologically significant applications.
2D materials↗
Characterization, Structure, and Reactivity of Hydroxyl Groups on Metal‐Oxide Cluster Nodes of Metal–Organic Frameworks: Structural Diversity and Keys to Reactivity and Catalysis
Among the most stable metal–organic frameworks (MOFs) are those incorporating nodes that are metal oxide clusters with frames such as Zr 6 O 8 . This review is a summary of the structure, bonding, and reactivity of MOF node hydroxyl groups, emphasizing those bonded to nodes containing aluminum and zirconium ions. Hydroxyl groups are often present on these nodes, sometimes balancing the charges of the metal ions. They arise during MOF syntheses in aqueous media or in post-synthesis treatments. They are identified with infrared and 1 H nuclear magnetic resonance spectroscopies and characterized by their reactivities with polar compounds such as alcohols. Terminal OH, paired µ 2 -OH, and aqua groups on nodes are catalytic sites in numerous reactions. Relatively unreactive hydroxyl groups (such as isolated µ 2 -OH groups) may replace reactive groups and inhibit catalysis; some node hydroxyl groups (e.g., µ 3 -OH) are mere spectators in catalysis. There are similarities between MOF node hydroxyl groups and those on the surfaces of bulk metal oxides, zeolites, and enzymes, but the comparisons are mostly inexact, and much remains to be understood about MOF node hydroxyl group chemistry. It is posited that understanding and controlling this chemistry will lead to tailored MOFs and improved adsorbents and catalysts.
36 MATERIALS SCIENCE↗
Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation
Abstract Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre‐prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room‐temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer‐wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze‐drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm −3 ), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.
Chemistry↗
Tunable Phonon Polariton Hybridization in a Van der Waals Hetero‐Bicrystal
Abstract Phonon polaritons, the hybrid quasiparticles resulting from the coupling of photons and lattice vibrations, have gained significant attention in the field of layered van der Waals heterostructures. Particular interest has been paid to hetero‐bicrystals composed of molybdenum oxide (MoO 3 ) and hexagonal boron nitride (hBN), which feature polariton dispersion tailorable via avoided polariton mode crossings. In this work, the polariton eigenmodes in MoO 3 ‐hBN hetero‐bicrystals self‐assembled on ultrasmooth gold are systematically studied using synchrotron infrared nanospectroscopy. It is experimentally demonstrated that the spectral gap in bicrystal dispersion and corresponding regimes of negative refraction can be tuned by material layer thickness, and these results are quantitatively matched with a simple analytic model. Polaritonic cavity modes and polariton propagation along “forbidden” directions are also investigated in microscale bicrystals, which arise from the finite in‐plane dimension of the synthesized MoO 3 micro‐ribbons. The findings shed light on the unique dispersion properties of polaritons in van der Waals heterostructures and pave the way for applications leveraging deeply sub‐wavelength mid‐infrared light‐matter interactions.
36 MATERIALS SCIENCE↗
Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products
Abstract Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure‐selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N 2 , reaching a current density of 20 mA cm geo −2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in‐situ spectroscopies and scattering experiments reveal a unique in situ generated Cu (2‐x)+ ‐OO −• active sites in CuCo, which initiates nucleophilic substitution of NH 2 from the amide, leading to N‐N coupling between * NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high‐valence Ni 3+ and Ni 4+ , which facilitates N‐H activation. This process, in conjunction with the excessive accumulation of OH − ions on Jahn‐Teller (JT) distorted Co sites, leads to the generation of NO 2 − as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.
36 MATERIALS SCIENCE↗
Freestanding Ammonium Vanadate Composite Cathodes with Lattice Self-Regulation and Ion Exchange for Long-Lasting Ca-Ion Batteries
Calcium-ion batteries (CIBs) have emerged as a promising alternative for electrochemical energy storage. The lack of high-performance cathode materials severely limits the development of CIBs. Vanadium oxides are particularly attractive as cathode materials for CIBs, and preinsertion chemistry is often used to improve their calcium storage performance. However, the room temperature cycling lifespan of vanadium oxides in organic electrolytes still falls short of 1000 cycles. Here, based on preinsertion chemistry, the cycling life of vanadium oxides is further improved by integrated electrode and electrolyte engineering. Utilizing a tailored Ca electrolyte, the constructed freestanding (NH 4 ) 2 V 6 O 16 ·1.35H 2 O@graphene oxide@carbon nanotube (NHVO-H@GO@CNT) composite cathode achieves a 305 mAh g -1 high capacity and 10 000 cycles record-long life. Additionally, for the first time, a Ca-ion hybrid capacitor full cell is assembled and delivers a capacity of 62.8 mAh g -1 . The calcium storage mechanism of NHVO-H@GO@CNT based on a two-phase reaction and the exchange of NH 4 + and Ca 2+ during cycling are revealed. The lattice self-regulation of V—O layers is observed and the layered vanadium oxides with Ca 2+ pillars formed by ion exchange exhibit higher capacity. This work provides novel strategies to enhance the calcium storage performance of vanadium oxides via integrated structural design of electrodes and electrolyte modification.
25 ENERGY STORAGE↗