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Using recent advances in X-ray microscopy, this study aimed to elucidate mechanisms of uptake, subcellular distribution, and translocation of functionalized CeO 2 MNM (manufactured nanomaterials), having different charges, by tomato plants ( Solanum lycopersicum cv Micro-Tom).
Mesogeometric anatomy – 2D inter-material surfaces and 1D skeletons – extracted from triply-periodic, double-gyroid network assembled from triblock copolymers.
Weakly-bound ligands in dynamic exchange expose the surface of CdSe quantum dots to pH-dependent modification.
We investigated the catalytic activity of different coating layers and put forward a selection criterion for surface layers. Al 2 O 3 could effectively suppress HER and enable the cycling of Li 4 Ti 5 O 12 anode in water-in-salt electrolyte, with a capacity of 145 mA h g −1 .
Well-defined organometallics supported on high surface area oxides are promising heterogeneous catalysts. An important design factor in these materials is how the metal interacts with the functionalities on an oxide support, commonly anionic X-type ligands derived from the reaction of an organometallic M–R with an –OH site on the oxide. The metal can either form a covalent M–O bond or form an electrostatic M + $\cdots$ – O ion-pair, which impacts how well-defined organometallics will interact with substrates in catalytic reactions. However, a less common reaction pathway involves the reaction of a Lewis site on the oxide with the organometallic, resulting in abstraction to form an ion-pair, which is relevant to industrial olefin polymerization catalysts. This Feature Article views the spectrum of reactivity between an organometallic and an oxide through the prism of Brønsted and/or Lewis acidity of surface sites and draws analogies to the molecular frame where Lewis and Brønsted acids are known to form reactive ion-pairs. Applications of the well-defined sites developed in this article are also discussed.
Single atom, low valent transition metals are important for heterogeneous catalysis but are challenging to generate and stabilize in a well-defined manner. Herein, we explored the functionalization of silica with well-defined N-heterocyclic phosphenium (NHP) ions to heterogenize low-valent metals. The surface electro-statically bound [NHP] + coordinate to Pt(0) precursors resulting in well-defined, chemisorbed [(NHP)Pt(0)L n ] + sites. The resulting materials catalyze the hydrosilylation of alkynes and exhibit activities and selectivities that rival the current industry standard homogeneous catalysts. The catalysts leach Pt limiting their recyclability; however, recycling studies support that the high regioselectivities arise from heterogeneous sites and Pt particles do not form on the surface. Here we suspect that this phosphenium-based immobilization strategy will result in stable, tunable, low valent heterogeneous transition metal catalysts in a wider array of catalytic reactions.
Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the S N 2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the S N 2 reaction.
Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81 S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.
Existing RF Surface Plasma Sources (SPS) for accelerators have specific efficiencies for H{sup +} and H{sup −} ion generation around 3 to 5 mA/cm{sup 2} per kW, where about 50 kW of RF power is typically needed for 50 mA beam current production. The Saddle Antenna (SA) SPS described here was developed to improve H{sup −} ion production efficiency and SPS reliability and availability. At low RF power, the efficiency of positive ion generation in the plasma has been improved to 200 mA/cm{sup 2} per kW of RF power at 13.56 MHz. Initial cesiation of the SPS was performed by heating cesium chromate cartridges by discharge as was done in the very first versions of the SPS. A small oven to decompose cesium compounds and alloys was developed and tested. After cesiation, the current of negative ions to the collector was increased from 1 mA to 10 mA with RF power ∼1.5 kW in the plasma (6 mm diameter emission aperture) and up to 30 mA with ∼4 kW RF power in the plasma and 250 Gauss longitudinal magnetic field. The ratio of electron current to negative ion current was improved from 30 to 2. Stable generation of H{sup −} beam without intensity degradation was demonstrated in the AlN discharge chamber for a long time at high discharge power in an RF SPS with an external antenna. Continuous wave (CW) operation of the SA SPS has been tested on the small test stand. The general design of the CW SA SPS is based on the pulsed version. Some modifications were made to improve the cooling and cesiation stability. The extracted collector current can be increased significantly by optimizing the longitudinal magnetic field in the discharge chamber. CW operation with negative ion extraction was tested with RF power up to 1.8 kW from the generator (∼1.2 kW in the plasma) with production up to Ic=7 mA. Long term operation was tested with 1.2 kW from the RF generator (∼0.8 kW in the plasma) with production of Ic=5 mA, Iex ∼15 mA (Uex=8 kV, Uc=14 kV)
There are currently few viable diagnostic techniques for in situ measurement of plasma facing component erosion. Digital holography is intended to fill this gap. Progress on the development of single and dual CO 2 laser digital holography diagnostics for in situ plasma facing component erosion is discussed. The dual laser mode’s synthetic wavelength allows the measurable range to be expanded by a factor of ~400 compared to single laser digital holography. This allows the diagnostic to measure surface height changes of up to 4.5 μm in single laser mode and up to 2 mm in dual laser mode. Results include ex situ measurements of plasma eroded targets and also dynamic measurements of nm and μm scale motion of a target mounted on a precision translation stage. Dynamic measurements have successfully been made with the system operating in both single and dual laser modes, from ~50 nm to ~4 μm in single laser mode and up to ~400 μm in dual laser mode (limited only by the stage speed and camera acquisition duration). These results demonstrate the feasibility of using digital holography to characterize plasma facing component erosion dynamically, i.e., during plasma exposure. Results of proof-of-principle in situ digital holographic measurements of targets exposed to an electrothermal arc plasma source are presented.
The ITER divertor will feature tungsten monoblocks as the plasma-facing component (PFC) that will be subject to extreme temperature and radiation environments. This paper reports the development of surface morphologies on tungsten under helium bombardment at high temperatures, which has important implications for safety, retention, and PFC erosion. Polycrystalline tungsten samples were implanted in the Dual Advanced Ion Simultaneous Implantation Experiment dual-beam ion implantation experiment at the University of Wisconsin-Madison with He-only and simultaneous He-D implantation at incidence angles of 55 deg, ion energies of 30 keV, and surface temperatures of 900°C to 1100°C. Morphologies resulting from angled incidence conditions differed from those produced under normal incidence bombardment at similar energy and temperature conditions in previous work. A variety of ordered and disordered morphologies dependent on grain orientation were observed for fluences up to 6 × 10 18 He cm –2 . These morphologies displayed dependencies on crystal orientation at low fluences and incident beam directions at higher fluences. Furthermore, these structures appeared, with variation, under both single-species He and mixed He-D implantations.
Widespread, high levels of tree mortality, termed forest die-off, associated with drought and rising temperatures, are disrupting forests worldwide. Drought will likely become more frequent with climate change, but even without more frequent drought, higher temperatures can exacerbate tree water stress. The temperature sensitivity of drought-induced mortality of tree species has been evaluated experimentally for only single-step changes in temperature (ambient compared to ambient + increase) rather than as a response surface (multiple levels of temperature increase), which constrains our ability to relate changes in the driver with the biological response. Here we show that time-to-mortality during drought for seedlings of two western United States tree species, Pinus edulis (Engelm.) and Pinus ponderosa (Douglas ex C. Lawson), declined in continuous proportion with increasing temperature spanning a 7.7 °C increase. Although P. edulis outlived P. ponderosa at all temperatures, both species had similar relative declines in time-to-mortality as temperature increased (5.2% per °C for P. edulis; 5.8% per °C for P. ponderosa). When combined with the non-linear frequency distribution of drought duration—many more short droughts than long droughts—these findings point to a progressive increase in mortality events with global change due to warming alone and independent of additional changes in future drought frequency distributions. As such, dire future forest recruitment patterns are projected assuming the calculated 7–9 seedling mortality events per species by 2100 under business-as-usual warming occur, congruent with additional vulnerability predicted for adult trees from stressors like pathogens and pests. Our progressive projection for increased mortality events was driven primarily by the non-linear shape of the drought duration frequency distribution, a common climate feature of drought-affected regions. These results illustrate profound benefits for reducing emissions of carbon to the atmosphere from anthropogenic sources and slowing warming as rapidly as possible to maximize forest persistence.
Here we investigate Ge mixing at the Si(001) surface and characterize the 2 N Si(001) reconstruction by means of hybrid quantum and molecular mechanics calculations (QM/MM). Avoiding fake elastic dampening, this scheme allows to correctly take into account long range deformation induced by reconstructed and defective surfaces. We focus in particular on the dimer vacancy line (DVL) and its interaction with Ge adatoms. We first show that calculated formation energies for these defects are highly dependent on the choice of chemical potential and that the latter must be chosen carefully. Characterizing the effect of the DVL on the deformation field, we also find that the DVL favors Ge segregation in the fourth layer close to the DVL. Using the activation-relaxation technique (ART nouveau) and QM/MM, we show that a complex diffusion path permits the substitution of the Ge atom in the fourth layer, with barriers compatible with mixing observed at intermediate temperature. We also show that the use of QM/MM results in much more signi cant corrections at the saddle points (up to 0.5 eV) that at minima, demonstrating its importance for describing kinetics correctly.
Here, we report a technique of a continuously doped surface of Bi 2 Sr 2 CaCu 2 O 8+x through ozone/vacuum annealing and a systematic measurement over the nearly whole superconducting dome on the same sample surface by in situ angle-resolved photoemission spectroscopy. We find that the quasiparticle weight on the antinode is proportional to the doped carrier concentration x within the entire superconducting dome, while the nodal quasiparticle weight changes more mildly. More significantly, we discover that a d-wave pairing energy gap extracted from the nodal region scales well with the onset temperature of the Nernst signal. These findings suggest that the emergence of superconducting pairing is concomitant with the onset of free vortices.
Abstract not provided
Semilocal density functional approximations are widely used. None of them can capture the long-range van der Waals (vdW) attraction between separated subsystems, but they differ remarkably in the extent to which they capture intermediate-range vdW effects responsible for equilibrium bonds between neighboring small closed-shell subsystems. The local density approximation (LDA) often overestimates this effect, while the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) underestimates it. The strongly constrained and appropriately normed (SCAN) meta-GGA often estimates it well. All of these semilocal functionals require an additive nonlocal correction such as the revised Vydrov-Van Voorhis 2010 (rVV10) to capture the long-range part. This work reports adsorption energies and the corresponding geometry of aromatic thiophene (C 4 H 4 S) bound to transition-metal surfaces. The adsorption process requires a genuine interplay of covalent and weak binding and requires a simultaneously accurate description of surface and adsorption energies with the correct prediction of the adsorption site. All these quantities must come from well-balanced short- and long-range correlation effects for a universally applicable method for weak interactions with chemical accuracy. Here, our methods indicate that the correct interplay is not present in any combination of recent meta-GGA's and rVV10. The simple short-range damping of the vdW correction scheme that is practically successful in the combination of GGA's and vdW approximations is less transferable in SCAN+rVV10 or in the revised version, revSCAN+rVV10. In addition, we present accurate random-phase-approximation-quality adsorption energies from a model based on the one of Zaremba and Kohn.
Not provided.
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