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Imaging of buried epitaxial InAs QDs as well as thin films of PbS QDs was carried out by means of local photocurrent measurements using a conductive atomic force microscope. InAs dots appear as dark areas in the photocurrent map and PbS:PCBM thin films form domain-like structures showing enhanced photoactivity.
To identify the role of waste composition and sediment interactions in controlling Pu and Am mobility in contaminated sediments at Hanford, a legacy nuclear site, Pu and Am concentrations in solutions equilibrated with contaminated sediments from beneath the 216-Z-9 (Z-9) Trench were compared to the solubilities of PuO 2 materials, synthesized by methods representative of the disposed wastes, in the absence of sediments. Furthermore, this work shows that the solubilities of PuO 2 materials synthesized by different methods, and with varying particle sizes, agree with PuO 2 (am,hyd), although dissolution kinetics differed between materials. According to saturation index (SI) calculations, PuO 2 (am,hyd) is likely also controlling Pu release from sediments under conditions where phosphate concentrations are low. However, both Pu-phosphate and Am-phosphate phases, identified in SI calculations and by high resolution transmission electron microscopy, play roles in controlling release in low pH, high phosphate, shallow sediments just below the Z-9 Trench. The elevated phosphate is likely due to decomposition of tributyl phosphate from waste solutions over time. Sediments from deeper in the subsurface beneath the Z-9 Trench are less acidic and contain less phosphate, with Pu solubility likely controlled by PuO 2 (am,hyd) that precipitated following neutralization of the acidic waste stream. Controls on Am concentrations in deeper sediments are more complex and potentially involve sediment adsorption and/or release from Pu (1-x) Am x O 2 following Am in-growth. The concentrations of both Pu and Am were elevated in the colloidal fraction associated with shallow sediments, but not in PuO 2 experiments, suggesting the presence of Pu/Am pseudocolloids (e.g., Pu/Am associated with mineral colloids). However, Pu and Am association with the colloidal size fraction was not observed in deeper sediments, suggesting transport of Pu and Am to these depths beneath the Z-9 Trench was not due to colloidal transport.
While highly reactive cerium oxide nanoparticles (CeO 2 NPs) are widely used in industry, their transport in aquatic systems is not well understood. To fill this knowledge gap, the interactions of CeO 2 NPs with arsenite (As 3+ ), a toxic metalloid and potential co-present contaminant, were investigated with respect to CeO 2 NP colloidal stability, dissolution, and surface redox reactions. Arsenite showed distinctive effects at different concentrations, with a high As 3+ concentration (10 –4 M) inducing 90% of CeO 2 NPs to settle from solution after 8 hours, while lower As 3+ concentrations (10 –5 or 10 –6 M) led to only 20% of CeO 2 NPs settling. The dissolution of NPs was most significant in the 10 –5 M As 3+ system owing to a lesser extent of aggregation, exposing more CeO 2 surface for dissolution. In the three As 3+ concentration systems, >97% of aqueous arsenic remained as As 3+ over 6 hours. On the NP surface, adsorbed As III was oxidized to As V , resulting in 58–70% of the adsorbed arsenic remaining as As III . Simultaneously Ce IV was reduced to Ce III , increasing Ce III on the CeO 2 NP surface from 17% (without arsenite) to 21–25% (with arsenite). Further mechanistic analyses revealed that the adsorption of arsenite was the main contributor to neutralizing the CeO 2 NP surface potential, enhancing particle sedimentation. These findings suggest that the fate and transport of CeO 2 NPs in our experimental systems are strongly affected by arsenite concentration and its adsorption on NPs. Here, the results also highlight the importance of the interplay between NP aggregation, oxidation, and dissolution in predicting the behaviors of CeO 2 NPs and associated toxic elements in aquatic systems.
Thin fluid layers confined between nanoparticles play an important role in several natural and industrial systems, including radioactive wastes stored in tanks at the U.S. Department of Energy’s Hanford site. Multimodal neutron and computational approaches have been integrated to examine the properties of one, two, and four layers of water (H 2 O or D 2 O) on nanoparticulate, hydrous, or deuterated boehmite (γ-AlOOH or γ-AlOOD). Exposure of deuterated boehmite to H 2 O at 90 °C yielded rapid H/D isotopic exchange likely driven by a Grotthus-like proton-hopping mechanism. The in-plane and out-of-plane vibrations of the structural hydroxyls involved in this exchange were observed for both the hydrated and deuterated boehmite. These observations were confirmed by molecular dynamics simulations that also showed that single water molecules on the (010) surface bond to the structure via four bonds: two from hydrogens (deuteriums) on the water to surrounding oxygens and two from the water’s oxygen to surrounding OD/OH. Bulk water-like properties began to appear once four monolayers of water had been added, but steric crowding limited water diffusion rates once two monolayers had been added. The super-Arrhenius temperature dependence observed at four monolayers indicated glass-like behavior in a well-formed hydrogen-bonding network. Such a network is not sufficiently developed, however, when the surface water coverage is less than four layers. In conclusion, the unique nature of these layers can provide critical information for understanding forces between particles in proximity, and resultant effects on suspension rheology.
The polymer brush architecture of the end-tethered polymer molecules is one of the most widely used efficient methods to regulate interfacial interactions in colloidal systems found in live matter and manufactured materials. Emerging applications of polymer brush structures require solutions to new tasks in the control of interfacial interactions. The rapid development of live cell manufacturing relies on scalable and efficient cell harvesting methods. Stimuli-responsive surfaces made of surface-grafted poly(N-isopropylacrylamide) (PNIPAM) can bind and detach the adherent cell upon changes in temperature and have been used for cell growth and harvesting. The applications are limited by the requirement to satisfy a range of PNIPAM coating characteristics that depend on the dimensions of the integrin complex in the cell membrane and the basal surface. The analysis of the microstructured surfaces, when adhesive and disjoining functions of the microdomains are decoupled, shows that many limitations of PNIPAM one-component coatings can be avoided by using a much broader range of structural characteristics of the microstructured interfaces composed of alternating disjoining PNIPAM domains and adhesive polymeric domains with cell-affinity functional groups. Temperature-controlled reversible adhesion to such microstructured interfaces is studied here experimentally with model systems of solid spherical particles and by employing simulations for solid and soft membranes interacting with the microstructured surfaces to mimic interactions with soft and solid disk-like particles.
Abstract not provided
We report a study combining x-ray photon correlation spectroscopy (XPCS) with in situ rheology to investigate the microscopic dynamics and mechanical properties of aqueous suspensions of the synthetic hectorite clay Laponite, which is composed of charged, nanometer-scale, disk-shaped particles. The suspensions, with particle concentrations ranging from 3.25 to 3.75 wt%, evolve over time from a fluid to a soft glass that displays aging behavior. The XPCS measurements characterize the localization of the particles during the formation and aging of the soft-glass state. The fraction of localized particles f 0 increases rapidly during the early formation stage and grows more slowly during subsequent aging, while the characteristic localization length r loc steadily de- creases. Despite the strongly varying rates of aging at different concentrations, both f 0 and r loc scale with the elastic shear modulus G' in a manner independent of concentration. During the later aging stage, the scaling between r loc and G' agrees quantitatively with a prediction of naive mode coupling theory. Breakdown of agreement with the theory during the early formation stage indi- cates the prevalence of dynamic heterogeneity, suggesting the soft solid forms through precursors of dynamically localized clusters.
Highlights: ► One-pot synthesis of ferrite magnetic nanoparticles (<10 nm) in non-polar media. ► Nanoparticles present high monocrystal quality and monodispersion. ► Superparamagnetic behavior at room temperature. ► Nanoparticles transfer to polar media via ligand exchange. - Abstract: An easy, efficient, reproducible and scalable one-pot synthetic methodology to obtain magnetic spinel ferrite nanoparticles has been developed. This approach is based on one-pot thermal decomposition of Fe(acac){sub 3} and M(acac){sub 2} (M = Co, Mn, Cu and Zn) in oleylamine, which also acts as a capping ligand, by producing stable colloidal dispersions of nanoparticles in non-polar solvents. The properties of the nanoparticles have been studied via different techniques, such as transmission electron microscopy, which shows that nanoparticles are monocrystallines and a narrow dispersion in size; magnetic analyses have demonstrated that the resulting ferrite nanoparticles show high saturation values and superparamagnetic behavior at room temperature; X-ray diffraction has also been performed, and it confirms that the synthesized nanoparticles have a spinel structure. Complementarily, ligand exchange has been also carried out in order to produce dispersions of the synthesized nanoparticles in polar media.
The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, silver-functionalized silica aerogel (Ag 0 -aerogel), shows promise as a potential replacement for silver mordenite because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag 0 -aerogel to a durable SiO 2 -based waste form makes this aerogel an attractive choice for sequestering radioiodine. The main purpose of the study reported here was to investigate consolidation of Ag 0 -aerogel powders with or without iodine and with or without sintering additives with hot uniaxial pressing (HUP), HIP, and SPS. The selected densified samples were analyzed with a helium gas pycnometer for apparent density, with the Archimedes method for open porosity and apparent density, with scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification, macro- and microstructural changes, and distribution of individual elements, and with X-ray diffraction (XRD) for crystalline phases. To convert the iodine-loaded Ag 0 -silica aerogel to a waste form, rapid consolidation with HUP, HIP, and SPS at moderate temperatures and pressures yields a final waste form consisting of AgI particles encapsulated in fused silica. HUP-processing (1200°C for 30 min under 29 MPa pressure) of Ag 0 -aerogel loaded with 20.2 mass% of iodine provided a product with residual open porosity of 16.9%. However, ~93% of sorbed iodine was retained in the sintered material. Densification with HIP at 1200°C for 30 min under 207 MPa pressure resulted in a fully dense silica-based waste form of 3.3 $\times$ 10 3 kg/m 3 bulk density containing ~22 mass% of iodine. Iodine was retained in the form of nano- and micro-inclusions of AgI dispersed in the silica matrix. Additives were not needed to enhance sintering process as depicted from the lack of open porosity and 100% retention of iodine in the consolidated product. The future tests will tell whether additives such as raw silica aerogel or Ag 0 -aerogel are required for HIPing to produce a fully dense waste form from iodine-loaded Ag 0 -aerogel containing higher concentrations of captured iodine. SPS-processing of samples with or without iodine revealed a benefit of additive-enhanced sintering. The samples containing additives (raw silica aerogel, colloidal silica, and Ag 0 -aerogel) shrunk faster and at lower temperatures. In addition, additives significantly improved distribution of silver compounds in the fully densified products, considerably decreasing the number of micron-sized inclusions of AgI, Ag and Ag 2 S at the grain boundaries.
In this paper we report the preparation of a modified electrode with gold nanoparticles and guanine. The colloidal suspension of gold nanoparticles was obtained by Turkevich method and was next analyzed by UV-Vis spectroscopy and Transmission Electron Microscopy (TEM). The gold electrode was modified by self-assembling the gold nanoparticles with guanine, the organic molecule playing also the role of linker. The electrochemical characteristics of the bare and modified electrode were investigated by Electrochemical Impedance Spectroscopy (EIS). A theoretical model was developed based on an electrical equivalent circuit which contain solution resistance (R{sub s}), charge transfer resistance (R{sub ct}), Warburg impedance (Z{sub W}) and double layer capacitance (C{sub dl})
Many-body interactions between polymer-grafted nanoparticles (NPs) play a key role in promoting their assembly into low-dimensional structures within polymer melts, even when the particles are spherical and isotropically grafted. However, capturing such interactions in simulations of NP assembly is very challenging because explicit modeling of the polymer grafts and melt chains is highly computationally expensive, even using coarse-grained models. Here, we develop a many-body potential for describing the effective interactions between spherical polymer-grafted NPs in a polymer matrix through a machine-learning approach. The approach involves using permutationally invariant polynomials to fit two- and three-body interactions derived from the potential of mean force calculations. The potential developed here reduces the computational cost by several orders of magnitude, thereby, allowing us to explore assembly behavior over large length and time scales. We show that the potential not only reproduces previously known assembled phases such as 1D strings and 2D hexagonal sheets, which generally cannot be achieved using isotropic two-body potentials, but can also help discover interesting phases such as networks, clusters, and gels. We demonstrate how each of these assembly morphologies intrinsically arises from a competition between two- and three-body interactions. Our approach for deriving many-body effective potentials can be readily extended to other colloidal systems, enabling researchers to make accurate predictions of their behavior and dissect the role of individual interaction energy terms of the overall potential in the observed behavior.
We present an integrated experimental and theoretical study of the dynamics and rheology of self-crosslinked, slightly charged, temperature responsive soft poly(N-isopropylacrylamide) (pNIPAM) microgels over a wide range of concentration and temperature spanning the sharp change in particle size and intermolecular interactions across the lower critical solution temperature (LCST). Dramatic, non-monotonic changes in viscoelasticity are observed as a function of temperature, with distinct concentration dependence in the dense fluid, glassy, and soft-jammed regimes. Motivated by our experimental observations, we formulate a minimalistic model for the size dependence of a single microgel particle and the change of the interparticle interaction from purely repulsive to attractive upon heating. Using microscopic equilibrium and time-dependent statistical mechanical theories, theoretical predictions are quantitatively compared with experimental measurements of the shear modulus. Good agreement is found for the nonmonotonic temperature behavior that originates as a consequence of the competition between reduced microgel packing fraction and increasing interparticle attractions. Furthermore, testable predictions are made for nonlinear rheological properties such as the yield stress and strain. To our knowledge, this is the first attempt to quantitatively understand in a unified manner the viscoelasticity of dense, temperature-responsive microgel suspensions spanning a wide range of temperatures and concentrations.
The drop-and-dry is a common technique allowing for creation of periodic nanoparticle (NP) structures for sensing, photonics, catalysis, etc. However, the reproducibility and scalability of this approach for fabrication of NP-based structures faces serious challenges due to the complexity of the simple, at first glance, evaporation process. In this work we study the effect of the spatial confinement on the NP self-assembly under slow solvent evaporation, when the air-liquid-substrate contact line (CL) expands from the center towards the walls of a cylindrical cell, forming a toroid. Using in situ video monitoring of the stick-slip CL motion, we find regular hydrodynamic perturbations in the meniscus, and reveal fine details of the formation of quasiperiodic rings of close packed NP layers. We report that drying of the toroidal NP droplet has a number of important differences from drying of the classical hemispherical colloidal drops. In toroidal drops we observe linear-in-time average meniscus motion, in contrast to the hemispherical drops where the meniscus moves as a square root of time. While both droplet geometries produce NP ring patterns, the ring width for the toroidal drop decreases with increasing ring radius, while it decreases with decreasing the radius of the hemispherical drop. We suggest that free ligands are the main cause of the Marangoni instabilities driving the periodic vorticity in the meniscus. Finally, we show that the usually ignored contact line tension may yield a considerable contribution to the CL pinning causing the CL slip-stick motion and the ring formation.
Indium phosphide quantum dots (InP QD) are a promising alternative to traditional QD materials that contain toxic heavy elements such as lead and cadmium. However, InP QD obtained from colloidal synthesis are often plagued by poor photoluminescence quantum yields (PL-QYs). In order to improve the PL-QY of InP QD, a number of post-synthetic treatments have been devised. Recently, it has been shown that InP post-synthetically treated with Lewis acid metal divalent cations (M-InP) exhibit enhanced PL-QY; however, the molecular structure and mechanism behind the improved PL-QY are not fully understood. Here, to determine the surface structure of M-InP QD, dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy (DNP SENS) experiments were employed on a series of InP magic size clusters treated with Cd ions, InP QD, cadmium phosphide (Cd 3 P 2 ) QD, and Cd-treated InP QD (Cd–InP QD). With the use of DNP SENS, we were able to obtain the 1D 31 P and 113 Cd NMR spectra, 113 Cd{ 31 P} rotational-echo double-resonance (REDOR) NMR spectra, and 31 P{ 113 Cd} dipolar heteronuclear multiple quantum correlation (D-HMQC) sequence. Changes in the phosphide 31 P chemical shifts after Cd treatment provide indirect evidence that some Cd alloys into the sub-surface regions of the particle. DNP-enhanced 113 Cd solid-state NMR spectra suggest that most Cd ions are coordinated by oxygen atoms from either carboxylate ligands or surface phosphate groups. 113 Cd{ 31 P} REDOR and 31 P{ 113 Cd} D-HMQC experiments confirm that a subset of Cd ions are located on the surface of Cd–InP QD and coordinated with phosphate groups.
Current lithium ion battery technology is tied in with conventional reaction mechanisms such as insertion, conversion, and alloying reactions even though most future applications like EVs demand much higher energy densities than current ones. Exploring the exceptional reaction mechanism and related electrode materials can be critical for pushing current battery technology to a next level. Here, we introduce an exceptional reaction with a Co(OH) 2 material which exhibits an initial charge capacity of 1112 mAh g –1 , about twice its theoretical value based on known conventional conversion reaction, and retains its first cycle capacity after 30 cycles. The combined results of synchrotron X-ray diffraction and X-ray absorption spectroscopy indicate that nanosized Co metal particles and LiOH are generated by conversion reaction at high voltages, and Co x H y , Li 2 O, and LiH are subsequently formed by hydride reaction between Co metal, LiOH, and other lithium species at low voltages, resulting in a anomalously high capacity beyond the theoretical capacity of Co(OH) 2 . This is further corroborated by AIMD simulations, localized STEM, and XPS. Furthermore, these findings will provide not only further understanding of exceptional lithium storage of recent nanostructured materials but also valuable guidance to develop advanced electrode materials with high energy density for next-generation batteries.
Colloidal silica structures are highly important for applications ranging from surface modifications such as superhydrophobic, oleophobic, icephobic, and anti-biofouling coatings, as reinforcements in polymer-ceramic or metal-matrix composites, and phonon management. In addition to various types of silica structures, a unique structure silica rods has been synthesized by employing the emulsion droplets made by dissolving polyvinlypyrrolidone in pentanol. While a significant progress has been made in further modifying their shape and chemistry, in their assembly, and in their applications, however, no review article compiled the progress in this field. Furthermore, this minireview intends to highlight the development in the synthesis, assembly, and application of these rods, and discuss the remaining challenges for precise control of size and shape, possible solutions, and potential applications.
We studied plasmonic features of bimetallic nanostructures consisting of gold nanoisland cores semi-coated with a chromium layer and explored how they influence emission of CdSe/ZnS quantum dots. We showed that, compared with chromium-covered glass substrates without the gold cores, the bimetallic nanostructures could significantly enhance the emission of the quantum dots. We studied the impact of the excitation intensity and thickness of the chromium layer on this process and utilized numerical means to identify the mechanisms behind it. Our results suggest that when the chromium layer is thin, the enhancement process is the result of the bimetallic plasmonic features of the nanostructures. As the chromium layer becomes thick, the impact of the gold cores is screened and the enhancement mostly happens mostly via the field enhancement of chromium nanoparticles in the absence of significant energy transfer from the quantum dots to these nanoparticles.
Colloidal quantum dot (CQD) solar cells have attracted tremendous attention mostly due to their wide absorption spectrum window and potentially low processability cost. The ultimate efficiency of CQD solar cells is highly limited by their high trap state density. Here in this paper we show that the overall device power conversion efficiency could be improved by employing photonic structures that enhance both charge generation and collection efficiencies. By employing a two-dimensional numerical model, we have calculated the characteristics of patterned CQD solar cells based of a simple grating structure. Our calculation predicts a power conversion efficiency as high as 11.2%, with a short circuit current density of 35.2 mA/cm 2 , a value nearly 1.5 times larger than the conventional flat design, showing the great potential value of patterned quantum dot solar cells.