Continuous synthesis of high-entropy alloy nanoparticles by in-flight alloying of elemental metals.

High-entropy alloy (HEA) nanoparticles (NPs) exhibit unusual combinations of functional properties. However, their scalable synthesis remains a significant challenge requiring extreme fabrication conditions. Metal salts are often employed as precursors because of their low decomposition temperatures, yet contain potential impurities. Here, we propose an ultrafast (< 100 ms), one-step method that enables the continuous synthesis of HEA NPs directly from elemental metal powders via in-flight alloying. A high-temperature plasma jet ( > 5000 K) is employed for rapid heating/cooling (103 - 105 K s-1), and demonstrates the synthesis of CrFeCoNiMo HEA NPs ( ~ 50 nm) at a high rate approaching 35 g h-1 with a conversion efficiency of 42%. Our thermofluid simulation reveals that the properties of HEA NPs can be tailored by the plasma gas which affects the thermal history of NPs. The HEA NPs demonstrate an excellent light absorption of > 96% over a wide spectrum, representing great potential for photothermal conversion of solar energy at large scales. Our work shows that the thermal plasma process developed could provide a promising route towards industrial scale production of HEA NPs.

Spontaneous formation of boron nitride nanotube fibers by boron impurity reduction in laser ablation of ammonia borane.

Highly crystalline and few-walled boron nitride nanotubes (BNNTs) had been synthesized by laser ablation using only ammonia borane as a precursor. As a molecular precursor, ammonia borane supplied both B and N atoms with a ratio of 1:1, and BNNTs were formed via the homogeneous nucleation of BN radicals, not the growth from boron nano-droplets, which is a generally accepted growth mechanism of the laser-grown BNNTs. Owing to the absence of amorphous boron impurities, the van der Waals interaction among BNNTs became effective and thus a BNNT fibers was formed spontaneously during the BNNT synthesis. The BNNT growth and the subsequent fiber formation are found to occur only at high pressures of a surrounding gas. The mechanism behind the critical role of pressure was elucidated from the perspective of reaction kinetics and thermal fluid behaviors. A polarized Raman study confirmed that the BNNT fiber formed exhibits a good alignment of BNNTs, which implies great potential for continuous production of high-quality BNNT fibers for various applications.

Insight into BN Impurity Formation during Boron Nitride Nanotube Synthesis by High-Temperature Plasma.

The high-temperature plasma process has demonstrated great potential in growing high-quality boron nitride nanotubes (BNNTs) with small diameters (∼5 nm) and few walls (3-4 walls) and led to successful commercialization with a high production rate approaching 20 g/h. However, the process is still accompanied by the production of BN impurities (e.g., a-BN, BN shell, BN flakes) whose physicochemical properties are similar to those of BNNTs. This renders the post-purification process very challenging and thus hampers the development of their practical applications. In this study, we have employed both experimental and numerical approaches for a mechanistic understanding of BN impurity formation in the high-temperature plasma process. This study suggests that the flow structure of the plasma jet (e.g., laminar or turbulent) plays a key role in the formation of BN impurities by dictating the transport phenomena of BNNT seeds (e.g., B droplets), which play an important role in BNNT nucleation. We discussed that the turbulence enhances the radial diffusion of B droplets as well as their interparticle coagulation, which leads to a significant reduction in the population of effective BNNT seeds in the BNNT growth zone (T < 4000 K). This results in the generation of unreacted BN precursors (e.g., B-N-H species) in the BNNT growth zone that eventually self-assemble into BN impurities. Our numerical simulation also suggests that a higher thermal energy input makes the flow more turbulent in the BNNT growth zone due to the elevated velocity difference between the plasma jet and ambient cold gas. This finding provides critical insight into the process design that can suppress the BN impurity formation in the high-temperature plasma process.

Enrichment of Semiconducting Single-Walled Carbon Nanotubes with Indigo-Fluorene-Based Copolymers and Their Use in Printed Thin-Film Transistors and Carbon Dioxide Gas Sensors.

High-purity semiconducting single-walled carbon nanotubes (sc-SWCNTs) are promising for portable and high-sensitivity gas sensors because of their excellent physical and electrical properties. Here, we describe the synthesis of a novel indigo-fluorene-based copolymer (PFIDBoc) that has been designed to selectively enrich sc-SWCNTs with excellent purity (>99.9%) yet contain a latent function in the form of a tert-butoxy (t-BOC)-protected amine that can be later revealed and exploited for carbon dioxide (CO2) gas sensing. SWCNTs wrapped with the PFIDBoc polymer can be easily converted via an on-chip thermal process to reveal a vinylogous amide moiety with a secondary amine nitrogen within the indigo building block of the copolymer which is perfectly suited for CO2 recognition. Thin-film transistors and sensors were inkjet-printed onto rigid and flexible substrates, demonstrating the versatility of enriched PFIDBoc-derived sc-SWCNT dispersions. The printed transistors exhibited a mobility up to 9 cm2 V-1 s-1 and on/off current ratios >105. We further demonstrate herein a CO2 sensor for indoor air quality monitoring even in low humidity environments, possessing a linear response with up to ∼5.4% sensitivity and a dynamic range between 400 and 2000 ppm in air with a relative humidity of ∼ 40%.

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design.

Increasing attention has been given to amine-copper formate complexes for their use as low-cost printable conductive inks. The structure of amine ligands coordinated to copper centers has been reported to dictate the properties of copper molecular inks, such as stability and printability, thereby influencing the copper reduction pathway during the thermolysis. Yet, the underlying mechanism by which formate is oxidized when complexed with amine ligands is still not fully understood. Here, we propose a mechanistic pathway of copper formate dehydrogenation and decarboxylation and examine the critical role that amine ligands play in their thermal decomposition by employing first-principles electronic structure computations and experimental analyses of thermolysis reactions. Based on the computational characterization of the relevant reaction pathways for a number of primary and secondary amines as well as pyridine ligand complexes, we are the first to show that the hydrogen bonds formed between the amine ligand and formate are the key factors governing the activation energy, providing a design principle for the synthesis of organic ligands that can tune the height of the reaction barriers of the dehydrogenation and decarboxylation reactions. The calculations, confirmed by NMR studies, show that the reduction of Cu(II) to Cu(I) occurs in concert with the release of H2 via the dimerization of Cu(II) hydride. This result suggests that the monomeric elimination of H2 is not favorable for the Cu(II) to Cu(I) reduction and thus identifies dimeric amino copper formate as an important intermediate for copper reduction whose thermodynamic stabilities are also dictated by the nature of the amine ligands.

Carbon Nanotubes and Related Nanomaterials: Critical Advances and Challenges for Synthesis toward Mainstream Commercial Applications.

Advances in the synthesis and scalable manufacturing of single-walled carbon nanotubes (SWCNTs) remain critical to realizing many important commercial applications. Here we review recent breakthroughs in the synthesis of SWCNTs and highlight key ongoing research areas and challenges. A few key applications that capitalize on the properties of SWCNTs are also reviewed with respect to the recent synthesis breakthroughs and ways in which synthesis science can enable advances in these applications. While the primary focus of this review is on the science framework of SWCNT growth, we draw connections to mechanisms underlying the synthesis of other 1D and 2D materials such as boron nitride nanotubes and graphene.

Role of Hydrogen in High-Yield Growth of Boron Nitride Nanotubes at Atmospheric Pressure by Induction Thermal Plasma.

We recently demonstrated scalable manufacturing of boron nitride nanotubes (BNNTs) directly from hexagonal BN (hBN) powder by using induction thermal plasma, with a high-yield rate approaching 20 g/h. The main finding was that the presence of hydrogen is crucial for the high-yield growth of BNNTs. Here we investigate the detailed role of hydrogen by numerical modeling and in situ optical emission spectroscopy (OES) and reveal that both the thermofluidic fields and chemical pathways are significantly altered by hydrogen in favor of rapid growth of BNNTs. The numerical simulation indicated improved particle heating and quenching rates (∼105 K/s) due to the high thermal conductivity of hydrogen over the temperature range of 3500-4000 K. These are crucial for the complete vaporization of the hBN feedstock and rapid formation of nanosized B droplets for the subsequent BNNT growth. Hydrogen is also found to extend the active BNNT growth zone toward the reactor downstream, maintaining the gas temperature above the B solidification limit (∼2300 K) by releasing the recombination heat of H atoms, which starts at 3800 K. The OES study revealed that H radicals also stabilize B or N radicals from dissociation of the feedstock as BH and NH radicals while suppressing the formation of N2 or N2+ species. Our density functional theory calculations showed that such radicals can provide faster chemical pathways for the formation of BN compared with relatively inert N2.

Covalent Functionalization of Boron Nitride Nanotubes via Reduction Chemistry.

Boron nitride nanotubes (BNNTs) exhibit a range of properties that hold great potential for many fields of science and technology; however, they have inherently low chemical reactivity, making functionalization for specific applications difficult. Here we propose that covalent functionalization of BNNTs via reduction chemistry could be a highly promising and viable strategy. Through density functional theory calculations of the electron affinity of BNNTs and their binding energies with various radicals, we reveal that their chemical reactivity can be significantly enhanced via reducing the nanotubes (i.e., negatively charging). For example, a 5.5-fold enhancement in reactivity of reduced BNNTs toward NH2 radicals was predicted relative to their neutral counterparts. The localization characteristics of the BNNT π electron system lead the excess electrons to fill the empty p orbitals of boron sites, which promote covalent bond formation with an unpaired electron from a radical molecule. In support of our theoretical findings, we also experimentally investigated the covalent alkylation of BNNTs via reduction chemistry using 1-bromohexane. The thermogravimetric measurements showed a considerable weight loss (12-14%) only for samples alkylated using reduced BNNTs, suggesting their significantly improved reactivity over neutral BNNTs. This finding will provide an insight in developing an effective route to chemical functionalization of BNNTs.

Theory of two-dimensional self-assembly of Janus colloids: crystallization and orientational ordering.

We study the rich crystalline phase behavior of amphiphilic spherical Janus colloids using a new formulation of self-consistent phonon theory that includes coupled translational and rotational entropic and enthalpic contributions to the free energy. In contrast to homogeneous spheres, broken rotational symmetry can result in more exotic crystals that possess distinct orientational patterns, and also plastic crystals. Ground states are identified based on the compatibility between the patch geometry of particles (e.g., patch coverage, number, shape) and lattice symmetry. We derive the explicit coupled self-consistent equations for translational and rotational localization parameters for effectively 2-dimensional dense monolayers of Janus crystals. The equations are numerically solved for a given crystal symmetry, thermodynamic state, and patch orientational order, and the thermodynamic stability of different phases is determined. For hexagonal packing, we predict with increasing temperature or decreasing attraction strength the possibility of a phase sequence of maximally bonded zigzag stripe, trimer, and rotationally disordered plastic crystal phases (or a phase sequence of trimer, dimer, and plastic crystal), which depends sensitively on particle chemical composition (Janus balance) and pressure. The role of rotational entropy in stabilizing the intermediate trimer (or dimer) phase at intermediate temperatures and high pressures is discussed in detail. Evolution of the center-of-mass vibrational and rotational amplitudes with thermodynamic state and Janus balance is also determined.

Self-consistent phonon theory of the crystallization and elasticity of attractive hard spheres.

We propose an Einstein-solid, self-consistent phonon theory for the crystal phase of hard spheres that interact via short-range attractions. The approach is first tested against the known behavior of hard spheres, and then applied to homogeneous particles that interact via short-range square well attractions and the Baxter adhesive hard sphere model. Given the crystal symmetry, packing fraction, and strength and range of attractive interactions, an effective harmonic potential experienced by a particle confined to its Wigner-Seitz cell and corresponding mean square vibrational amplitude are self-consistently calculated. The crystal free energy is then computed and, using separate information about the fluid phase free energy, phase diagrams constructed, including a first-order solid-solid phase transition and its associated critical point. The simple theory qualitatively captures all the many distinctive features of the phase diagram (critical and triple point, crystal-fluid re-entrancy, low-density coexistence curve) as a function of attraction range, and overall is in good semi-quantitative agreement with simulation. Knowledge of the particle localization length allows the crystal shear modulus to be estimated based on elementary ideas. Excellent predictions are obtained for the hard sphere crystal. Expanded and condensed face-centered cubic crystals are found to have qualitatively different elastic responses to varying attraction strength or temperature. As temperature increases, the expanded entropic solid stiffens, while the energy-controlled, fully-bonded dense solid softens.

Morphology of nematic and smectic vesicles.

Recent experiments on vesicles formed from block copolymers with liquid-crystalline side chains reveal a rich variety of vesicle morphologies. The additional internal order ("structure") developed by these self-assembled block copolymer vesicles can lead to significantly deformed vesicles as a result of the delicate interplay between two-dimensional ordering and vesicle shape. The inevitable topological defects in structured vesicles of spherical topology also play an essential role in controlling the final vesicle morphology. Here we develop a minimal theoretical model for the morphology of the membrane structure with internal nematic/smectic order. Using both analytic and numerical approaches, we show that the possible low free energy morphologies include nano-size cylindrical micelles (nano-fibers), faceted tetrahedral vesicles, and ellipsoidal vesicles, as well as cylindrical vesicles. The tetrahedral vesicle is a particularly fascinating example of a faceted liquid-crystalline membrane. Faceted liquid vesicles may lead to the design of supramolecular structures with tetrahedral symmetry and new classes of nano-carriers.

Structural reorganization of parallel actin bundles by crosslinking proteins: incommensurate states of twist.

We construct a coarse-grained model of parallel actin bundles crosslinked by compact globular bundling proteins, such as fascin and espin, necessary components of filopodial and mechanosensory bundles. Consistent with structural observations of bundles, we find that the optimal geometry for crosslinking is overtwisted, requiring a coherent structural change of the helical geometry of the filaments. We study the linker-dependent thermodynamic transition of bundled actin filaments from their native state to the overtwisted state and map out the "twist-state" phase diagram in terms of the availability as well as the flexibility of crosslinker proteins. We predict that the transition from the uncrosslinked to fully crosslinked state is highly sensitive to linker flexibility: flexible crosslinking smoothly distorts the twist state of bundled filaments, while rigidly crosslinked bundles undergo a phase transition, rapidly overtwisting filaments over a narrow range of free crosslinker concentrations. Additionally, we predict a rich spectrum of intermediate structures, composed of alternating domains of sparsely bound (untwisted) and strongly bound (overtwisted) filaments. This model reveals that subtle differences in crosslinking agents themselves modify not only the detailed structure of parallel actin bundles, but also the thermodynamic pathway by which they form.

Cooperativity and frustration in protein-mediated parallel actin bundles.

We examine the mechanism of bundling of cytoskeletal actin filaments by two representative bundling proteins, fascin and espin. Small-angle x-ray studies show that increased binding from linkers drives a systematic overtwist of actin filaments from their native state, which occurs in a linker-dependent fashion. Fascin bundles actin into a continuous spectrum of intermediate twist states, while espin only allows for untwisted actin filaments and fully overtwisted bundles. Based on a coarse-grained, statistical model of protein binding, we show that the interplay between binding geometry and the intrinsic flexibility of linkers mediates cooperative binding in the bundle. We attribute the respective continuous (discontinuous) bundling mechanisms of fascin (espin) to difference in the stiffness of linker bonds themselves.

Topological defects in spherical nematics.

We study the organization of topological defects in a system of nematogens confined to the two-dimensional sphere (S2). We first perform Monte Carlo simulations of a fluid system of hard rods (spherocylinders) living in the tangent plane of S2. The sphere is adiabatically compressed until we reach a jammed nematic state with maximum packing density. The nematic state exhibits four +1/2 disclinations arrayed on a great circle. This arises from the high elastic anisotropy of the system in which splay (K1) is far softer than bending (K3). We also introduce and study a lattice nematic model on S2 with tunable elastic constants and map out the preferred defect locations as a function of elastic anisotropy. We find a one-parameter family of degenerate ground states in the extreme splay-dominated limit K_{3}/K_{1}-->infinity. Thus the global defect geometry is controllable by tuning the relative splay to bend modulus.

Bubble-raft model for a paraboloidal crystal.

We investigate crystalline order on a two-dimensional paraboloid of revolution by assembling a single layer of millimeter-sized soap bubbles on the surface of a rotating liquid, thus extending the classic work of Bragg and Nye on planar soap bubble rafts. Topological constraints require crystalline configurations to contain a certain minimum number of topological defects such as disclinations or grain boundary scars whose structure is analyzed as a function of the aspect ratio of the paraboloid. We find the defect structure to agree with theoretical predictions and propose a mechanism for scar nucleation in the presence of large Gaussian curvature.

Interstitial fractionalization and spherical crystallography.

Finding the ground states of identical particles packed on spheres has relevance for stabilizing emulsions and has a venerable history in the literature of theoretical physics and mathematics. Theory and experiment have confirmed that defects such as disclinations and dislocations are an intrinsic part of the ground state. Here we discuss the remarkable behavior of vacancies and interstitials in spherical crystals. The strain fields of isolated disclinations forced in by the spherical topology literally rip interstitials and vacancies apart, typically into dislocation fragments that combine with the disclinations to create small grain-boundary scars. The fractionalization is often into three charge-neutral dislocations, although dislocation pairs can be created as well. We use a powerful, freely-available computer program to explore interstitial fractionalization in some detail, for a variety of power-law pair potentials. We investigate the dependence on initial conditions and the final state energies, and compare the position dependence of interstitial energies with the predictions of continuum elastic theory on the sphere. The theory predicts that, before fragmentation, interstitials are repelled and vacancies are attracted from 5-fold disclinations. We also use vacancies and interstitials to study low-energy states in the vicinity of "magic numbers" that accommodate regular icosadeltahedral tessellations.

Dynamics and instabilities of defects in two-dimensional crystals on curved backgrounds.

Point defects are ubiquitous in two-dimensional crystals and play a fundamental role in determining their mechanical and thermodynamical properties. When crystals are formed on a curved background, finite-length grain boundaries (scars) are generally needed to stabilize the crystal. We provide a continuum elasticity analysis of defect dynamics in curved crystals. By exploiting the fact that any point defect can be obtained as an appropriate combination of disclinations, we provide an analytical determination of the elastic spring constants of dislocations within scars and compare them with existing experimental measurements from optical microscopy. We further show that vacancies and interstitials, which are stable defects in flat crystals, are generally unstable in curved geometries. This observation explains why vacancies or interstitials are never found in equilibrium spherical crystals. We finish with some further implications for experiments and future theoretical work.