Hydrogen bonding and molecular orientations across thin water films on sapphire
Not Available
Boily, Jean-François↗
SEARCH · Engineering Papers
Results for “waters”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Effect of Cu2+ Activation on Interfacial Water Structure at the Sphalerite Surface as Studied by Molecular Dynamics Simulation
In the first part of this paper, an experimental contact angle study of the fresh and Cu2+ activated sphalerite-ZnS surface as well as the covellite-CuS (001) surface is reported describing the increased hydrophobic character of the surface during Cu2+ activation. In addition to these experimental results, the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite- CuS2 (100), and covellite-CuS (001) surfaces were examined using Molecular Dynamics Simulation (MDS). Our MDS results on the behavior of interfacial water at the fresh sphalerite-ZnS (110), copper-zinc sulfide-CuZnS2 (110), villamaninite-CuS2 (100), and covellite-CuS (001) surfaces include simulated contact angles, water number density distribution, water dipole orientation, water residence time, and hydrogen-bonding considerations. The copper content at the Cu2+ activated sphalerite surface seems to account for the increased hydrophobicity as revealed by both experimental and MD simulated contact angle measurements. The relatively greater hydrophobic character developed at the Cu2+ activated sphalerite surface and at the copper-zinc sulfide surface has been described by MDS, based on the structure of interfacial water and its dynamic properties. L.X.D. acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.
Jin, Jiaqi↗
Integrating computation and experiment to investigate photoelectrodes for solar water splitting at the microscopic scale.
CONSPECTUS: Photoelectrochemical water-splitting is a promising and sustainable way to store the energy of the sun in chemical bonds and use it to produce hydrogen gas, a clean fuel. The key components in photoelectrochemical cells (PECs) are photoelectrodes, including a photocathode that reduces water to hydrogen gas and a photoanode that oxidizes water to oxygen gas. Materials used in photoelectrodes for PECs must effectively absorb sunlight, yield photogenerated carriers, and exhibit electronic properties that enable the efficient shuttling of carriers to the surface to participate in relevant water-splitting reactions. Discovering and understanding the key characteristics of optimal photoelectrode materials is paramount to the realization of PEC technologies. Oxide-based photoelectrodes can satisfy many of these materials requirements, including stability in aqueous environments, band edges with reasonable alignment with the redox potentials for water splitting, and ease of synthesis. However, oxide photoelectrodes generally suffer from poor charge transport properties and considerable bulk electron-hole separation, and they have relatively large band gaps. Numerous strategies have been proposed to improve these aspects and understand how these improvements are reflected in the photoelectrochemical performance. Unfortunately, the structural and compositional complexity of multinary oxides accompanied by the inherent complexity of photoelectrochemical processes makes it challenging to understand the individual effects of composition, structure, and defects in the bulk and on the surface on a material's photoelectrochemical properties. The integration of experiment and theory has great potential to increase our atomic-level understanding of structure-composition-property relationships in oxide photoelectrodes. In this Account, we describe how integrating experiment and theory is beneficial for achieving scientific insights at the microscopic scale. We highlight studies focused on understanding the role of (i) bulk composition via solid-state solutions, intercalation, and comparison with isoelectronic compounds, (ii) dopants for both the anion and cation and their interactions with oxygen vacancies, and (iii) surface/interface structure in the photocurrent generation and photoelectrochemical performance in oxide photoelectrodes. In each instance, we outline strategies and considerations for integrating experiment and theory and describe how this integration led to valuable insights and new directions in uncovering structure-composition-property relationships. Our aim is to demonstrate the unique value of combining experiment and theory in studying photoelectrodes and to encourage the continued effort to bring experiment and theory in closer step with each other.
Wang, Wennie↗
The many-body expansion for aqueous systems revisited: 1. Water-water interactions
We revisit the Many-Body Expansion (MBE) for water-water interactions by examining the effects of the basis set, including those resulting from the Basis Set Superposition Error (BSSE) correction, on the various terms for selected sizes of water clusters up to n = 21. The analysis is performed at the second order Møller-Plesset (MP2) perturbation theory with the family of augmented correlation consistent basis sets up to five zeta quality for the (H2O)n, n = 7, 10, 13, 16 and 21 clusters, for which we report either the complete MBE (n = 7, 10) or the one through the 6-body (n = 13) and the 5-body terms (n = 16, 21). Our results suggest that any sizeable contributions to the total cluster binding energy arising from the 5-body and larger terms are solely an artifact of the size of the basis set. Indeed, all terms above the 4-body converge monotonically to practically zero at the Complete Basis Set (CBS) limit. The magnitudes of the 5-body and above terms are accurately reproduced even with the smaller basis set of the series (aug-cc-pVDZ) once the BSSE correction is taken into account. The same level of theory (MP2/aug-cc-pVDZ, BSSEcorrected) also accurately reproduces the MP2/CBS values of the 3- and 4-body terms. The contribution of electron correlation to the 3- and 4-body terms is quite small, so that neglecting the correlation contribution in all terms above the 3-body results in an error of ??(0.1%). The BSSE correction to the largest 2-body term in the MBE was accurately estimated from the function ?? [1 + erf(-?? ??)], which is proportional to the common (overlapping) area between two Gaussian distributions whose centers are separated by R, with the constants ??, ?? fitted to the calculated BSSE corrections for the individual 2-body terms of the clusters with each basis set. Our results unquestionably demonstrate that the MBE for water-water interactions converges to the 4-body term, since any finite terms above the 4-body are artifacts of the size of the basis set and can be safely truncated at the 4-body term when either a very large basis set is used or BSSE corrections are taken into account even with the aug-cc-pVDZ basis set. We expect these findings to have important consequences in the pursuit of accurate many-body molecular dynamics simulations for aqueous systems.
Heindel, Joseph↗
Mineral–Water Interface Structure of Xenotime (YPO 4 ) {100}
Crystal truncation rod (CTR) measurements and density functional theory (DFT) calculations were performed to determine the atomic structure of the mineral–water interface of the {100} surface of xenotime (nominally YPO 4 ). This mineral is important, because it incorporates a variety of rare earth elements (REEs) in its crystal structure. REEs are critical materials necessary for a variety of renewable and energy efficient technologies. Current beneficiation techniques are not highly selective for REE ore minerals, and large amounts go to waste; this is a first step toward designing more efficient beneficiation. Evidence is found for minor relaxation of the surface within the topmost monolayer with little or no relaxation in subsurface layers. Justification for ordered water at the interface is found, where water binds to surface cations and donates hydrogen bonds to surface phosphates. The average bond lengths between cations and oxygens on water are 228 pm in the best fit to the CTR data, versus 243 and 251 pm for the DFT. No agreement on water positions bound to surface phosphates is obtained. Altogether, the findings suggest that ligands used in beneficiation with a single anionic headgroup, such as fatty acids, will have limited selectivity for xenotime relative to undesirable minerals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Subtle Effects of Aliphatic Alcohol Structure on Water Extraction and Solute Aggregation in Biphasic Water/ n -Dodecane
Organic phase aggregation behavior of 1-octanol and its structural isomer, 2-ethylhexanol, in a biphasic n-dodecane water system is studied with a combination of physical measurement, small-angle X-ray scattering (SAXS), and atomistic molecular dynamic simulations. Physical properties of the organic phases are probed following their mixing and equilibration with immiscible water phases. Studies reveal that the interfacial tension decreases as a function of increasing alcohol concentration over the solubility range of the alcohol with no evidence for a critical aggregate concentration (cac). An uptake of water into the organic phases is quantified, as a function of alcohol content, by Karl Fischer titrations. The extraction of water into dodecane was further assessed as a function of alcohol concentration via the slope-analysis method sometimes employed in chemical separations. This provides a qualitative understanding of solute (water/alcohol) aggregation in the organic phase. The physical results are supported by analyses of SAXS data that reveals an emergence of aggregates in n-dodecane at elevated alcohol concentrations. The observed aggregate structure is dependent on the alcohol tail group geometry, consistent with surfactant packing parameter. The formation of these aggregates is discussed at a molecular level, where alcohol-alcohol and alcohol-water H-bonding interactions likely dominate the occurrence and morphology of the aggregates.
Knight, Andrew W.↗
Thick Layered Semiconductor Devices with Water Top-Gates: High On–Off Ratio Field-Effect Transistors and Aqueous Sensors
Layered semiconductors show promise as channel materials for field-effect transistors (FETs). Usually, such devices incorporate solid back or top gate dielectrics. Here, we explore deionized (DI) water as a solution top-gate for field-effect switching of layered semiconductors including SnS 2 , MoS 2 , and black phosphorus. The DI water gate is easily fabricated, can sustain rapid bias changes, and its efficient coupling to layered materials provides high on–off current ratios, near-ideal subthreshold swing, and enhanced short-channel behavior even for FETs with thick, bulk-like channels, where such control is difficult to realize with conventional back gating. Screening by the high-k solution gate eliminates hysteresis due to surface and interface trap states and substantially enhances the field-effect mobility. The onset of water electrolysis sets the ultimate limit to DI water gating at large negative gate bias. Measurements in this regime show promise for aqueous sensing, demonstrated here by the amperometric detection of glucose in aqueous solution. In conclusion, DI water gating of layered semiconductors can be harnessed in research on novel materials and devices, and it may with further development find broad applications in microelectronics and sensing.
36 MATERIALS SCIENCE↗
Stable Unassisted Solar Water Splitting on Semiconductor Photocathodes Protected by Multifunctional GaN Nanostructures
Producing hydrogen by unassisted solar water splitting is one essential step to make direct solar fuel conversion a viable energy source. To date, however, there has been no demonstration of stable photoelectrodes for high efficiency photoelectrochemical water splitting. In this work, we report that a GaInP2/GaAs/Ge triple-junction (3J) photocathode protected by multi-functional GaN nanostructures can enable both efficient and relatively stable solar water splitting. A 12.6% solar-to-hydrogen (STH) efficiency is measured without any external bias. Of particular importance, we demonstrate relatively stable solar water splitting for 80 hours in three-electrode configuration and 57 hours in two-electrode measurement at zero bias. This is the best reported stability for multi-junction semiconductor photocathodes in two-electrode configuration to our knowledge. Here, the multifunctional GaN nanostructure significantly reduces the charge transfer resistance at semiconductor/electrolyte interface and protects III-V materials against corrosion. Such multi-functional GaN photocatalytic nanostructures provide a new pathway to improve the performance of conventional photoelectrodes to achieve both efficient and stable unassisted solar water splitting.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Water‐Induced Diamond Formation at Earth's Core‐Mantle Boundary
Abstract The carbon and water cycles in the Earth's interior are linked to key planetary processes, such as mantle melting, degassing, chemical differentiation, and advection. However, the role of water in the carbon exchange between the mantle and core is not well known. Here, we show experimental results of a reaction between Fe 3 C and H 2 O at pressures and temperatures of the deep mantle and core‐mantle boundary (CMB). The reaction produces diamond, FeO, and FeH x , suggesting that water can liberate carbon from the core in the form of diamond (“core carbon extraction”) while the core gains hydrogen, if subducted water reaches to the CMB. Therefore, Earth's deep water and carbon cycles can be linked. The extracted core carbon can explain a significant amount of the present‐day mantle carbon. Also, if diamond can be collected by mantle flow in the region, it can result in unusually high seismic‐velocity structures.
Ko, Byeongkwan↗
Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction
The interaction of water vapor with ZnO/CuO x /Cu(1 1 1) surfaces was explored using synchrotron-based ambient pressure x-ray photoelectron spectroscopy (AP-XPS) and density-functional theory (DFT) calculations. Cu(1 1 1) does not dissociate the water molecule. Cleavage of O–H bonds was seen with AP-XPS after depositing ZnO or preparing CuO x on the copper substrate. The findings of DFT calculations show unique behavior for ZnO/CuO x /Cu(1 1 1), not seen on Cu(1 1 1), CuO x /Cu(1 1 1) or ZnO(0 0 0). The ZnO/CuO x /Cu(1 1 1) system binds water quite well and exhibits the lowest energy barrier for O–H bond cleavage. The presence of unsaturated Zn cations in the islands of ZnO led to high chemical reactivity. In order to remove the OH from ZnO/CuO x /Cu(1 1 1) and ZnO/Cu(1 1 1) surfaces, heating to elevated temperatures was necessary. At 500–600 K, a significant coverage of OH groups was still present on the surfaces and did react with CO during the water–gas shift (WGS) process. The final state of the sample depended strongly on the amount of ZnO present on the catalyst surface. For surfaces with a ZnO coverage below 0.3 ML, the adsorption of water did not change the integrity of the ZnO islands. On the other hand, for surfaces with a ZnO coverage above 0.3 ML, a ZnO→Zn x OH transformation was observed. This transformation led to a decrease in the WGS catalytic activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Comment on “Boson Peak in Deeply Cooled Confined Water: A Possible Way to Explore the Existence of the Liquid-to-Liquid Transition in Water”
In their Letter, Wang et al. report on an inelastic neutron scattering (INS) experiment where they describe the pressure evolution of a low energy (E ~ 6 meV) excitation, emerging in confined protonated water only below 230 K at an exchanged momentum Q=2.0 Å -1 . Also, water confinement was used to overcome the unavoidable crystallization occurring below ~250 K in bulk water. The authors report that a similar finding was also obtained in both bulk (numerical simulations) and confined water at ambient pressure. They refer to this low temperature excitation as a boson peak (BP), and relate its occurrence to the Widom line, concluding that the observed pressure behavior of the BP reveals the signature of the high-density liquid (HDL) to the low-density liquid (LDL) transition proposed, though severely questioned, for bulk water. Lastly, we believe these claims to be unconvincing for the following reasons.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The pervasive and multifaceted influence of biocrusts on water in the world's drylands
Not provided.
Biodiversity & Conservation↗
Synthesis of Cation and Water Free Cryptomelane Type OMS-2 Cathode Materials: The Impact of Tunnel Water on Electrochemistry
Cryptomelane type manganese dioxides (α-MnO 2 , OMS-2) are interesting potential cathode materials due to the ability of their one dimensional (1D) tunnels to reversibly host various cations including Li + and an accessible stable 3+/4+ redox couple. Here, we synthesized metal cation free OMS-2 materials where the tunnels were occupied by only water and hydronium ions. Water was subsequently removed from the tunnels. Cation free OMS-2 and Dry-OMS-2 were used as cathodes in Li based batteries to investigate the role of tunnel water on their electrochemistry. The initial discharge capacity was higher for Dry-OMS-2 (252 mAh/g) compared to OMS-2 (194 mAh/g), however, after 100 cycles Dry-OMS-2 and OMS-2 delivered 137 mAh/g and 134 mAh/g, respectively. Li + ion diffusion was more facile for Dry-OMS as evidenced by rate capability, at 400 mA/g. Dry-OMS-2 delivered 135mAh/g whereas OMS-2 delivered ~115 mAh/g. This first report of the impact of tunnel water on the electrochemistry of OMS-2 type materials demonstrates that the presence of tunnel water in OMS-2 type materials negatively impacts the electrochemistry.
energy storage (including batteries and capacitors↗
Transport and Transformation of Selenium and Other Constituents of Flue‐Gas Desulfurization Wastewater in Water‐Saturated Soil Materials
Constructed wetland treatment systems are used to remove selenium (Se) from flue‐gas desulfurization (FGD) wastewater (WW). However, direct confirmation of the mechanism responsible for FGD WW Se retention in soil is lacking. A laboratory‐based soil column study was performed to develop an evidence‐based mechanism of Se retention and to study the behavior and the retention capacity of FGD WW constituents in water‐saturated soil. A deoxygenated 1:1 mixture of FGD WW and raw water was delivered to the columns bottom‐up at a flux of 1.68 cm d −1 for 100 d. Some of the columns were flushed with the raw water at the same rate for an additional 100 d. Column effluent was analyzed for constituents of concern. Results showed a complete retention of FGD WW Se in the soil materials. Boron and fluorine were partially retained; however, sulfur, sodium, and chlorine retention was poor, agreeing with field observations. The FGD WW Se was retained in soil near the inlet end of the columns, indicating its limited mobility under reduced conditions. Sequential extraction procedure revealed that retained Se was mainly sequestered as stable/residual forms. Bulk‐ and micro‐X‐ray absorption near‐edge structure spectroscopy confirmed that Se was mainly retained as reduced/stable species [Se(IV), organic Se, and Se(0)]. This study provides direct evidence for FGD WW Se retention in water‐saturated soil via the transformation of oxidized Se into reduced/stable forms. Core Ideas The mechanism of FGD wastewater Se retention in water‐saturated soil was studied. Sequential fractionation of Se, micro‐XRF, and micro‐ and bulk‐XANES were used. Behavior of FGD wastewater constituents in saturated soil was comparable to field‐scale observations. FGD wastewater Se exhibited strong retention in reduced soil. Reduced/stable species of Se governed the retention mechanism.
Galkaduwa, Madhubhashini B.↗
Water Cycle-Driven Infectious Diseases as Multiscale, Reliable, Continuously Updating Water Cycle Sensors
We propose a novel synthesis of observational and simulated data (climatological and biological) to enhance understanding of the real-world interplay between climate (here, the water cycle) and the epidemiology of water cycle-driven infectious disease. Aligning with Focal Area 2, predictive modeling using AI techniques, we will develop systems of hierarchical models to discover latent features of the water cycle. Our approach will leverage state-of-the-art in Artificial Intelligence (AI) to measure the degree to which climate change-driven shifts in water cycle can be predicted by supplementing sparse and irregular climate data with water cycle-driven infectious disease resources.
54 ENVIRONMENTAL SCIENCES↗
Catalytic Reduction of Graphene Oxide Membranes and Water Selective Channel Formation in Water–Alcohol Separations
Graphene oxide (GO) is a promising membrane system for chemical separation applications due to its 2-D nanofluidics properties and an ability to control interplanar spacing for selectivity. The permeance of water, methanol (MeOH) and isopropyl alcohol (IPA) through 5 µm thick membranes was found to be 0.38 ± 0.15, 0.33 ± 0.16 and 0.42 ± 0.31 LMH/bar (liter/m2·h·bar), respectively. Interestingly, the permeance of a water–alcohol mixture was found to be dramatically lower (~0.01 LMH/bar) than any of its components. Upon removing the solvent mixture, the transmembrane flux of the pure solvent was recovered to near the original permeance. The interlayer space of a dried GO membrane was found to be 8.52 Å, which increased to 12.19 Å. 13.26 Å and 16.20 Å upon addition of water, MeOH and IPA. A decrease in d-space, about 2 Å, was consistently observed when adding alcohol to water wetted GO membrane and an optical color change and reduction in permeance. A newly proposed mechanism of a partial reduction of GO through a catalytic reaction with the water–alcohol mixture is consistent with experimental observations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Water-stress-induced breakdown of carbon–water relations: indicators from diurnal FLUXNET patterns
Understanding of terrestrial carbon and water cycles is currently hampered by an uncertainty in how to capture the large variety of plant responses to drought. In FLUXNET, the global network of CO 2 and H 2 O flux observations, many sites do not uniformly report the ancillary variables needed to study drought response physiology. To this end, we outline two data-driven indicators based on diurnal energy, water, and carbon flux patterns derived directly from the eddy covariance data and based on theorized physiological responses to hydraulic and non-stomatal limitations.Hydraulic limitations (i.e. intra-plant limitations on water movement) are proxied using the relative diurnal centroid ( C ET * ), whichmeasures the degree to which the flux of evapotranspiration (ET) is shiftedtoward the morning. Non-stomatal limitations (e.g. inhibitions of biochemical reactions, RuBisCO activity, and/or mesophyll conductance) are characterized by the Diurnal Water–Carbon Index (DWCI), which measures the degree of coupling between ET and gross primary productivity (GPP) within each day.As a proof of concept we show the response of the metrics at six European sites during the 2003 heat wave event, showing a varied response of morning shifts and decoupling. Globally, we found indications of hydraulic limitations in the form of significantly high frequencies of morning-shifted days in dry/Mediterranean climates and savanna/evergreen plant functional types (PFTs), whereas high frequencies of decoupling were dominated by dry climates and grassland/savanna PFTs indicating a prevalence of non-stomatal limitations in these ecosystems. Wholly, both the diurnal centroid and DWCI were associated with high net radiation and low latent energy typical of drought. Using three water use efficiency (WUE) models, we found the mean differences between expected and observed WUE to be - 0.09 to0.44 µ mol mmol -1 and - 0.29 to - 0.40 µ mol mmol -1 for decoupled and morning-shifted days, respectively, compared to mean differences - 1.41 to - 1.42 µ mol mmol -1 in dry conditions, suggesting that morning shifts/hydraulic responses are associated with an increase in WUE,whereas decoupling/non-stomatal limitations are not.
58 GEOSCIENCES↗