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At least 1,657 records · Page 92

The effect of shear flow on the rotational diffusion of a single axisymmetric particle

Understanding the orientation dynamics of anisotropic colloidal particles is important for suspension rheology and particle self-assembly. However, even for the simplest case of dilute suspensions in shear flow, the orientation dynamics of non-spherical Brownian particles are poorly understood. Here we analytically calculate the time-dependent orientation distributions for non-spherical axisymmetric particles confined to rotate in the flow–gradient plane, in the limit of small but non-zero Brownian diffusivity. For continuous shear, despite the complicated dynamics arising from the particle rotations, we find a coordinate change that maps the orientation dynamics to a diffusion equation with a remarkably simple ratio of the enhanced rotary diffusivity to the zero shear diffusion: $D_{eff}^{r}/D_{0}^{r}=(3/8)(p-1/p)^{2}+1$ , where $p$ is the particle aspect ratio. For oscillatory shear, the enhanced diffusion becomes orientation dependent and drastically alters the long-time orientation distributions. We describe a general method for solving the time-dependent oscillatory shear distributions and finding the effective diffusion constant. As an illustration, we use this method to solve for the diffusion and distributions in the case of triangle-wave oscillatory shear and find that they depend strongly on the strain amplitude and particle aspect ratio. These results provide new insight into the time-dependent rheology of suspensions of anisotropic particles. For continuous shear, we find two distinct diffusive time scales in the rheology that scale separately with aspect ratio $p$, as $1/D_{0}^{r}p^{4}$ and as $1/D_{0}^{r}p^{2}$ for $p\gg$ 1. For oscillatory shear flows, the intrinsic viscosity oscillates with the strain amplitude. Finally, we show the relevance of our results to real suspensions in which particles can rotate freely. Collectively, the interplay between shear-induced rotations and diffusion has rich structure and strong effects: for a particle with aspect ratio 10, the oscillatory shear intrinsic viscosity varies by a factor of ${\approx}2$ and the rotational diffusion by a factor of ${\approx}40$.

42 ENGINEERING↗

Structure and Hydration of Highly-Branched, Monodisperse Phytoglycogen Nanoparticles

Phytoglycogen is a naturally occurring polysaccharide nanoparticle made up of extensively branched glucose monomers. It has a number of unusual and advantageous properties, such as high water retention, low viscosity, and high stability in water, which make this biomaterial a promising candidate for a wide variety of applications. For this paper, we have characterized the structure and hydration of aqueous dispersions of phytoglycogen nanoparticles using neutron scattering. Small angle neutron scattering results suggest that the phytoglycogen nanoparticles behave similar to hard sphere colloids and are hydrated by a large number of water molecules (each nanoparticle contains between 250% and 285% of its mass in water). This suggests that phytoglycogen is an ideal sample in which to study the dynamics of hydration water. To this end, we used quasielastic neutron scattering (QENS) to provide an independent and consistent measure of the hydration number, and to estimate the retardation factor (or degree of water slow-down) for hydration water translational motions. These data demonstrate a length-scale dependence in the measured retardation factors that clarifies the origin of discrepancies between retardation factor values reported for hydration water using different experimental techniques. Finally, the present approach can be generalized to other systems containing nanoconfined water.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Humic Acid on the Removal of Chromium(VI) and the Production of Solids in Iron Electrocoagulation

Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1–200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. In our work, X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Protein Coatings Dictate the Dispersibility and Stability of Hydrophobic Zeolitic-Imidazolate Frameworks in Water

Metal–organic frameworks are promising materials for many biomedical technologies due to their ability to store and release large quantities of guest molecules in a predictable and tunable fashion. In biological fluids, proteins readily adsorb to the external surfaces of metal–organic framework particles through a combination of hydrophobic and electrostatic interactions. However, much remains to be understood about the nature of these protein coatings and how they influence the bulk properties of aqueous dispersions of metal–organic frameworks. Here, in this work, we show that a variety of proteins can be used to manipulate the properties of aqueous dispersions of zeolitic-imidazolate framework (ZIF) particles. Specifically, noncovalently associated protein coatings promote the formation of dispersions of hydrophobic ZIFs in water with high colloidal and hydrolytic stability, as long as the density of adsorbed proteins exceeds a critical, protein-dependent threshold. Further, these dispersions feature low viscosity and complete retention of gas carrying capacity. The wide range of properties accessible with protein coatings provides a highly modular approach to design hydrophobic metal–organic frameworks with properties tailored for specific biological applications.

adsorption↗

Ultrafast Dynamics of Plasmon-Coupled Excitons in Semiconducting Nanoplatelets

Exciton-plasmon coupling in nanomaterials produces many relevant phenomena for photonics applications including increased light-matter interactions, enhanced radiative rates of quantum emitters, and coherent energy exchange. In the case of exciton coupling to surface plasmon polaritons (SPPs), dispersive interactions controlled by the wavevector of optical excitation create the opportunity for tunable optical emission. Strong temporal impacts on exciton lifetimes can also occur in coupled systems, creating the opportunity for ultrafast control of exciton lifetime via changes in electronic coupling magnitude to a dispersive SPP. The coupling strength can be impacted by the morphology of the nanomaterials. Here, in this study, we utilize colloidal semiconductor nanoplatelets deposited onto thin silver plasmonic films, and compare the results to semiconductor quantum dots deposited on the silver films. We map the dispersion of the coupled systems and measure the ultrafast transient absorption response of the coupled systems. Due to the larger interaction areas of the nanoplatelets that lie flat on the silver films, a greater degree of coupling is found for the nanoplatelets, and much faster temporal responses are found as compared to quantum dots. Fresnel theory calculations that incorporate heavy and light hole features can reproduce the dispersion of the nanoplatelet-silver film, and a simple three-state model is developed to provide insights into the nature of the coupling at different photon energies along the dispersion curve.

colloidal semiconductor nanoplatelets↗

Salt-Induced Universal Slowing Down of the Short-Time Self-Diffusion of a Globular Protein in Aqueous Solution

The short-time self-diffusion D of the globular model protein bovine serum albumin in aqueous (D 2 O) solutions has been measured comprehensively as a function of the protein and trivalent salt (YCl 3 ) concentration, noted c p and c s , respectively. We observe that D follows a universal master curve D(c s ,c p ) = D(c s = 0,c p ) g(c s /c p ), where D(c s = 0,c p ) is the diffusion coefficient in the absence of salt and g(c s /c p ) is a scalar function solely depending on the ratio of the salt and protein concentration. This observation is consistent with a universal scaling of the bonding probability in a picture of cluster formation of patchy particles. In conclusion, the finding corroborates the predictive power of the description of proteins as colloids with distinct attractive ion-activated surface patches.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ion-Specific Effects on PuO 2 Nanoparticle Aggregation and Dissolution in Concentrated Electrolytes

Hydrolytic PuO 2 nanoparticles (NPs) are a dominant aqueous Pu-bearing phase in high ionic strength nuclear wastes, yet their reactivity in nonideal brines remains poorly constrained. We quantify how electrolyte identity and concentration control PuO 2 NP aggregation and ligand-assisted dissolution in acidic, high salinity solutions (NaCl, NaNO 3 , NaClO 4 , Na 2 SO 4 , Na 2 C 2 O 4 up to 5 M). A multitechnique workflow combining liquid scintillation counting (operationally defined aqueous [Pu]), scattering/electrokinetic measurements (aggregate size and zeta potential), and spectroscopy (UV–vis, XPS, Raman) resolves electrolyte-dependent partitioning between colloidal and molecular Pu species. Weakly coordinating anions (ClO 4 – , Cl – , NO 3 – ) largely preserve the (aggregated) nanoparticulate fraction but generate distinct dissolved species at high concentration, i.e., Pu(IV)–nitrato complexes in NaNO 3 and Pu(VI)–chloro complexes in NaCl. In contrast, stronger ligands substantially perturb PuO 2 NP stability: sulfate promotes partial dissolution to Pu(IV)–sulfate complexes at low concentration but reduces aqueous [Pu] at higher sulfate levels via secondary Pu(IV) sulfate formation, whereas oxalate drives strong dissolution to aqueous Pu–oxalate complexes. Aged NPs show similar trends with reduced aqueous fractions and more dominant aggregation mechanisms. In conclusion, these spectroscopically constrained speciation data provide a foundation for incorporating PuO 2 NP reactivity into thermodynamic and reactive transport models for high salinity waste and brine environments.

Aggregation↗

Mie-Resonant Three-Dimensional Metacrystals

Optical metamaterials, engineered to exhibit electromagnetic properties not found in natural materials, may enable new light-based applications including cloaking and optical computing. While there have been significant advances in the fabrication of two-dimensional metasurfaces, planar structures create nontrivial angular and polarization sensitivities, making omnidirectional operation impossible. Although three-dimensional (3D) metamaterials have been proposed, their fabrication remains challenging. In this work, we use colloidal crystal engineering with DNA to prepare isotropic 3D metacrystals from Au nanocubes. We show that such structures can exhibit refractive indices as large as ~8 in the mid-infrared, far greater than that of common high-index dielectrics. Additionally, we report the first observation of multipolar Mie resonances in metacrystals with well-formed habits, occurring in the mid-infrared for sub-micron metacrystals, which we measured using synchrotron infrared microspectroscopy. Finally, we predict that arrays of metacrystals could exhibit negative refraction. The results present a promising platform for engineering devices with unnatural optical properties.

3D metamaterials↗

High-Mobility Hole Transport in Single-Grain PbSe Quantum Dot Superlattice Transistors

Epitaxially-fused superlattices of colloidal quantum dots (QD epi-SLs) may exhibit electronic minibands and high-mobility charge transport, but electrical measurements of epi-SLs have been limited to large-area, polycrystalline samples in which superlattice grain boundaries and intragrain defects suppress/obscure miniband effects. Systematic measurements of charge transport in individual, highly-ordered epi-SL grains would facilitate the study of minibands in QD films. Here, we demonstrate the air-free fabrication of microscale field-effect transistors (μ-FETs) with channels consisting of single PbSe QD epi-SL grains (2–7 μm channel dimensions) and analyze charge transport in these single-grain devices. The eight devices studied show p-channel or ambipolar transport with a hole mobility as high as 3.5 cm 2 V –1 s –1 at 290 K and 6.5 cm 2 V –1 s –1 at 170–220 K, one order of magnitude larger than that of previous QD solids. The mobility peaks at 150–220 K, but device hysteresis at higher temperatures makes the true mobility–temperature curve uncertain and evidence for miniband transport inconclusive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence for Enhanced Tracer Diffusion in Densely Packed Interfacial Assemblies of Hairy Nanoparticles

Nearly monodisperse nanoparticle (NP) spheres attached to a nonvolatile ionic liquid surface were tracked by in situ scanning electron microscopy to obtain the tracer diffusion coefficient D tr as a function of the areal fraction Φ. The in situ technique resolved both tracer (gold) and background (silica) particles for ~1–2 min, highlighting their mechanisms of diffusion, which were strongly dependent on Φ. Structure and dynamics at low and moderate Φ paralleled those reported for larger colloidal spheres, showing an increase in order and a decrease in D tr by over 4 orders of magnitude. However, ligand interactions were more important near jamming, leading to different caging and jamming dynamics for smaller NPs. Finally, the normalized D tr at ultrahigh Φ depended on particle diameter and ligand molecular weight. Increasing the PEG molecular weight by a factor of 4 increased D tr by 2 orders of magnitude at ultrahigh Φ, indicating stronger ligand lubrication for smaller particles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Numerical Simulation of Light to Heat Conversion by Plasmonic Nanoheaters

Plasmonic nanoparticles are widely recognized as photothermal conversion agents, i.e., nanotransducers or nanoheaters. Translation of these materials into practical applications requires quantitative analyses of their photothermal conversion efficiencies (η). However, the value of η obtained for different materials is dramatically influenced by the experimental setup and method of calculation. Here, we evaluate the most common methods for estimating η (Roper’s and Wang’s) and compare these with numerical estimates using the simulation software ANSYS. Experiments were performed with colloidal gold nanorod solutions suspended in a hanging droplet irradiated by an 808 nm diode laser and monitored by a thermal camera. The ANSYS simulations accounted for both heating and evaporation, providing η values consistent with the Wang method but higher than the Roper approach. This study details methods for estimating the photothermal efficiency and finds ANSYS to be a robust tool where experimental constraints complicate traditional methods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reversible, Tunable, Electric-Field Driven Assembly of Silver Nanocrystal Superlattices

Nanocrystal superlattices are typically fabricated by either solvent evaporation or destabilization methods that require long time periods to generate highly ordered structures. In this paper, we report for the first time the use of electric fields to reversibly drive nanocrystal assembly into superlattices without changing solvent volume or composition, and show that this method only takes 20 min to produce polyhedral colloidal crystals, which would otherwise need days or weeks. This method offers a way to control the lattice constants and degree of preferential orientation for superlattices and can suppress the uniaxial superlattice contraction associated with solvent evaporation. As a result, in situ small-angle X-ray scattering experiments indicated that nanocrystal superlattices were formed while solvated, not during drying.

36 MATERIALS SCIENCE↗

Negatively Charged Excitons in CdSe Nanoplatelets

The low-temperature emission spectrum of CdSe colloidal nanoplatelets (NPLs) consists of two narrow lines. The high-energy line stems from the recombination of neutral excitons. The origin of the low-energy line is currently debated. Here, we experimentally study the spectral shift, emission dynamics, and spin polarization of both lines at low temperatures down to 1.5 K and in high magnetic fields up to 60 T and show that the low-energy line originates from the recombination of negatively charged excitons (trions). This assignment is confirmed by the NPL photocharging dynamics and associated variations in the spectrum. We show that the negatively charged excitons are considerably less sensitive to the presence of surface spins than the neutral excitons. The trion binding energy in three-monolayer-thick NPLs is as large as 30 meV, which is 4 times larger than its value in the two-dimensional limit of a conventional CdSe quantum well confined between semiconductor barriers. A considerable part of this enhancement is gained by the dielectric enhancement effect, which is due to the small dielectric constant of the environment surrounding the NPLs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High Thermoelectric Performance in 2D Sb 2 Te 3 and Bi 2 Te 3 Nanoplate Composites Enabled by Energy Carrier Filtering and Low Thermal Conductivity

Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb 2 Te 3 and Bi 2 Te 3 , are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb 2 Te 3 and Bi 2 Te 3 , were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb 2 Te 3 and Bi 2 Te 3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi 2 Te 3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 μV/K for 15% Bi 2 Te 3 . The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ~ 1.26, for the 15% Bi 2 Te 3 nanoplate composite at 450 K.

36 MATERIALS SCIENCE↗

Impact of Platinum Primary Particle Loading on Fuel Cell Performance: Insights from Catalyst/Ionomer Ink Interactions

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. Here, by investigating the CL gas-transport resistance and zeta-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink zeta-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, zeta-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

30 DIRECT ENERGY CONVERSION↗

Self-Assembly of Monodisperse Starburst Carbon Spheres into Hierarchically Organized Nanostructured Supercapacitor Electrodes

We report a three-dimensional (3D) porous carbon electrode containing both nanoscale and microscale porosity, which has been hierarchically organized to provide efficient ion and electron transport. The electrode organization is provided via the colloidal self-assembly of monodisperse starburst carbon spheres (MSCSs). The periodic close-packing of the MSCSs provides continuous pores inside the 3D structure that facilitate ion and electron transport (electrode electrical conductivity ~0.35 S m –1 ), and the internal meso- and micropores of the MSCS provide a good specific capacitance. Here, the capacitance of the 3D-ordered porous MSCS electrode is ~58 F g –1 at 0.58 A g –1 , 48% larger than that of disordered MSCS electrode at the same rate. At 1 A g –1 the capacitance of the ordered electrode is 57 F g –1 (95% of the 0.24 A g –1 value), which is 64% greater than the capacitance of the disordered electrode at the same rate. The ordered electrode preserves 95% of its initial capacitance after 4000 charging/discharging cycles.

25 ENERGY STORAGE↗

Elucidating the Microscale Behavior and Phase Separation Kinetics of Thermally Responsive Ionic Liquid–Water Mixtures

Thermally responsive ionic liquids (ILs) exhibit liquid-liquid phase separation into a water-rich (WR) and ionic-liquid-rich (ILR) phase when heated above a lower critical solution temperature (LCST). This phase behavior has been leveraged for applications ranging from forward osmosis (FO) desalination, where the IL acts as a draw solute, to refrigeration and dehumidification cycles, where the IL acts as a liquid desiccant. While significant effort has been devoted to characterizing the thermodynamic and thermophysical properties of LCST ILs, their phase separation kinetics have not been investigated. In this work, we describe the macroscale phase separation kinetics (phase separation time) by gleaning insight into the microscale colloidal behavior of aqueous mixtures of four different materials, P 4444 TFA (tetrabutylphosphonium-2,4-trifluoroacetate), P 4444 DMBS (tetrabutylphosphonium-2,4-dimethyl-benzenesulfonate), N 4444 Sal (tetrabutylammonium salicylate), and P 4444 Sal (tetrabutylphosphonium salicylate) as a function of IL concentration at a separation temperature of 70 °C. We report the discontinuous microscale size distributions for each material and correlate their theoretical settling velocities to experimental phase separation times. The results indicate that a simple Stokes' law model can predict the phase separation time within reasonable accuracy. Overall, this work lays the foundation for understanding the micro- to macroscale phase separation behavior and kinetics of LCST ILs for various water-energy applications.

LCST↗

Modular Pd/Zeolite Composites Demonstrating the Key Role of Support Hydrophobic/Hydrophilic Character in Methane Catalytic Combustion

Complete catalytic oxidation of methane in the presence of steam at low temperatures (T < 400 °C) is a crucial reaction for emission control, yet it presents profound challenges. The activation of the strong C–H bond of methane at low temperature is difficult, and the water present in any realistic application poisons the active surface and promotes sintering of Pd particles during the reaction. Finding materials that can deliver high reaction rates while being more resistant to the presence of water is imperative for advancing several technological applications of natural gas-based systems. However, methods to fairly compare the activity of Pd catalysts (the most active metal for methane combustion) are needed in order to perform useful structure–property relationship studies. Here in this paper, we report a method to study how zeolite hydrophobicity affects the activity of Pd nanoparticles in the reaction, which led to a significant improvement in the water resistance. Mesoporous zeolites were synthesized starting from commercially available microporous zeolites. In this way, a variety of hierarchically porous zeolites, with different hydrophobic/hydrophilic character, were prepared. Preformed colloidal Pd nanoparticles could be deposited within mesostructured zeolites. This approach enabled the systematic study of key parameters such as zeolite framework, Al content, and the Pd loading while maintaining the same Pd particle size and structure for all the samples. Detailed catalytic studies revealed an optimum hydrophobic/hydrophilic character, and a promising steam-resistant catalyst, namely, 3.2 nm Pd particles supported on mesoporous zeolite beta or USY with a Si/Al ratio of 40, emerged from this multiparametric study with a T 50 of 355 °C and T 90 of 375 °C (where T 50 and T 90 are temperature values at which the samples reach 50% and 90% methane conversion, respectively) in steam-containing reaction conditions. Finally, we verified that the designed catalysts were stable by in-depth postcatalysis characterization and operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) analyses confirming that water adsorbs less strongly on the active PdO surface due to interaction with the zeolite acid sites. This method can be of general use to study how zeolite supports affect the reactivity of supported metals in several catalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗