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DOE OSTI2022

Toroidal modeling of runaway electron loss due to 3D fields in ITER

Mitigation of runaway electrons (REs) by three-dimensional (3D) magnetic field perturbations is numerically investigated for the ITER 15 MA baseline D–T scenario, utilizing the MARS-F code (Liu et al Phys. Plasmas 7 3681) with a drift orbit test particle tracing module. Considered are two types of 3D fields: the n = 3 (n is the toroidal mode number) resonant magnetic perturbation (RMP) utilized for the purpose of controlling the edge localized modes in ITER, and perturbations generated by the n = 1 magneto-hydrodynamic (MHD) instabilities in a post-disruption plasma. The RMP field, applied to a pre-disruption plasma, is found to be moderately effective in mitigating the RE seeds in ITER when vacuum field model is assumed. Up to ~40% loss fraction is possible at 90 kA-turn coil current. The mitigation efficiency is however substantially reduced, down to less than 5%, when the plasma response is taken into account. This is due to strong screening of the resonant magnetic field components by the plasma response resulting in much less field line stochasticity. On the other hand, the MARS-F modeling, based on the DINA-simulated post-disruption equilibria, shows that the n = 1 resistive kink instabilities develop in these plasmas, as the edge safety factor qa evolves and drops below integer numbers. RE mitigation by these MHD instabilities is sensitive to the eigenmode structure. The best mitigation is achieved as q a drops below 3, when a global kink instability occurs that encompasses both internal and external components. This global instability is found to be capable of mitigating over 80% MeV-level passing RE orbits at a field perturbation |δB|/B 0 that is comparable to that observed in DIII-D experiments, and full mitigation if the perturbation amplitude is doubled. The 'wetted' area on the ITER limiting surface, due to MHD instability induced RE loss, generally increases with the perturbation amplitude (together with increasing loss fraction). At the highest perturbation level assumed in this study, the wetted area reaches ~60% of the total limiting surface area. Lastly, the lost RE orbits mainly strike the outer divertor region of the limiting surface, with some fraction also hitting a wide area along the inboard side of the surface.

3D fields↗

NASA NTRS1982

Capillary forces exerted by liquid drops caught between crossed cylinders. A 3-D meniscus problem with free contact line

The Young-Laplace equation is solved for three-dimensional menisci between crossed cylinders, with either the contact line fixed or the contact angle prescribed, by means of the Galerkin/finite element method. Shapes are computed, and with them the practically important quantities: drop volume, wetted area, capillary pressure force, surface tension force, and the total force exerted by the drop on each cylinder. The results show that total capillary force between cylinders increases with decreasing contact angle, i.e. with better wetting. Capillary force is also increases with decreasing drop volume, approaching an asymptotic limit. However, the wetted area on each cylinder decreases with decreasing drop volume, which raises the question of the optimum drop volume to strive for, when permanent bonding is sought from solidified liquid. For then the strength of the bond is likely to depend upon the area of contact, which is the wetted area when the bonding agent was introduced in liquid form.

Patzek, T. W.↗

NASA NTRS1999

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Robinson, M. B.↗

NASA NTRS1990

Modeling of surface roughness effects on glaze ice accretion

A series of experimental investigations focused on studying the cause and effect of roughness on accreting glaze ice surfaces were conducted. Detailed microvideo observations were made of glaze ice accretions on 1 to 4 inch diameter cylinders in three icing wind tunnels (the Data Products of New England six inch test facility, the NASA Lewis Icing Research Tunnel, and the B. F. Goodrich Ice Protection Research Facility). Infrared thermal video recordings were made of accreting ice surfaces in the Goodrich facility. Distinct zones of surface water behavior were observed; a smooth wet zone in the stagnation region with a uniform water film; a rough zone where surface tension effects caused coalescence of surface water into stationary beads; a horn zone where roughness elements grow into horn shapes; a runback zone where surface water ran back as rivulets; and a dry zone where rime feathers formed. The location of the transition from the smooth to the rough zone was found to migrate with time towards the stagnation point. The behavior of the transition appeared to be controlled by boundary layer transition and bead formation mechanisms at the interface between the smooth and rough zones. Regions of wet ice growth and enhanced heat transfer were clearly visible in the infrared video recordings of glaze ice surfaces. A simple multi-zone modification to the current glaze ice accretion model was proposed to include spatial variability in surface roughness.

Hansman, R. John, Jr.↗

DOE OSTI2021

Switchable wetting of oxygen-evolving oxide catalysts

The surface wettability of catalysts is typically controlled via surface treatments that promote catalytic performance. Here we report on potential-regulated hydrophobicity/hydrophilicity at cobalt-based oxide interfaces with an alkaline solution. The switchable wetting of single particles, directly related to their activity and stability towards the oxygen evolution reaction, was revealed by electrochemical liquid-phase transmission electron microscopy. Analysis of the movement of the liquid in real time revealed distinctive wettability behaviour associated with specific potential ranges. At low potentials, an overall reduction of the hydrophobicity of the oxides was probed. Upon reversible reconstruction towards the surface oxyhydroxide phase, electrowetting was found to cause a change in the interfacial capacitance. At high potentials, the evolution of molecular oxygen, confirmed by operando electron energy-loss spectroscopy, was accompanied by a globally thinner liquid layer. This work directly links the physical wetting with the chemical oxygen evolution reaction of single particles, providing fundamental insights into solid–liquid interfacial interactions of oxygen-evolving oxides.

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NASA NTRS1993

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Plumlee, G. S.↗

NASA NTRS1999

Snowmelt and Infiltration Deficiencies of SSiB and Their Resolution with a New Snow-Physics Scheme

A two-year 1987-1988 integration of SSiB forced with ISLSCP Initiative I surface data (as part of the Global Soil Wetness Project, GSWP, evaluation and intercomparison) produced generally realistic land surface fluxes and hydrology. Nevertheless, the evaluation also helped to identify some of the deficiencies of the current version of the Simplified Simple Biosphere (SSiB) model. The simulated snowmelt was delayed in most regions, along with excessive runoff and lack of an spring soil moisture recharge. The SSIB model had previously been noted to have a problem producing accurate soil moisture as compared to observations in the Russian snowmelt region. Similarly, various GSWP implementations of SSIB found deficiencies in this region of the simulated soil moisture and runoff as compared to other non-SSiB land-surface models (LSMs). The origin of these deficiencies was: 1) excessive cooling of the snow and ground, and 2) deep frozen soil disallowing snowmelt infiltration. The problem was most severe in regions that experience very cold winters. In SSiB, snow was treated as a unified layer with the first soil layer, causing soil and snow to cool together in the winter months, as opposed to snow cover acting as an insulator. In the spring season, a large amount of heat was required to thaw a hard frozen snow plus deep soil layers, delaying snowmelt and causing meltwater to become runoff over the frozen soil rather than infiltrate into it.

Sud, Y. C.↗

NASA NTRS2011

Analysis of the Dryden Wet Bulb GLobe Temperature Algorithm for White Sands Missile Range

In locations where workforce is exposed to high relative humidity and light winds, heat stress is a significant concern. Such is the case at the White Sands Missile Range in New Mexico. Heat stress is depicted by the wet bulb globe temperature, which is the official measurement used by the American Conference of Governmental Industrial Hygienists. The wet bulb globe temperature is measured by an instrument which was designed to be portable and needing routine maintenance. As an alternative form for measuring the wet bulb globe temperature, algorithms have been created to calculate the wet bulb globe temperature from basic meteorological observations. The algorithms are location dependent; therefore a specific algorithm is usually not suitable for multiple locations. Due to climatology similarities, the algorithm developed for use at the Dryden Flight Research Center was applied to data from the White Sands Missile Range. A study was performed that compared a wet bulb globe instrument to data from two Surface Atmospheric Measurement Systems that was applied to the Dryden wet bulb globe temperature algorithm. The period of study was from June to September of2009, with focus being applied from 0900 to 1800, local time. Analysis showed that the algorithm worked well, with a few exceptions. The algorithm becomes less accurate to the measurement when the dew point temperature is over 10 Celsius. Cloud cover also has a significant effect on the measured wet bulb globe temperature. The algorithm does not show red and black heat stress flags well due to shorter time scales of such events. The results of this study show that it is plausible that the Dryden Flight Research wet bulb globe temperature algorithm is compatible with the White Sands Missile Range, except for when there are increased dew point temperatures and cloud cover or precipitation. During such occasions, the wet bulb globe temperature instrument would be the preferred method of measurement. Out of the 30 dates examined, 23 fell under the category of having good accuracy.

LaQuay, Ryan Matthew↗

DOE OSTI2021

Effect of surface properties and polymer chain length on polymer adsorption in solution

In polymer nanoparticle composites (PNCs) with attractive interactions between nanoparticles (NPs) and polymers, a bound layer of the polymer forms on the NP surface, with significant effects on the macroscopic properties of the PNCs. The adsorption and wetting behaviors of polymer solutions in the presence of a solid surface are critical to the fabrication process of PNCs. In this study, we use both classical density functional theory (cDFT) and molecular dynamics (MD) simulations to study dilute and semi-dilute solutions of short polymer chains near a solid surface. Using cDFT, we calculate the equilibrium properties of polymer solutions near a flat surface while varying the solvent quality, surface–fluid interactions, and the polymer chain lengths to investigate their effects on the polymer adsorption and wetting transitions. Using MD simulations, we simulate polymer solutions near solid surfaces with three different curvatures (a flat surface and NPs with two radii) to study the static conformation of the polymer bound layer near the surface and the dynamic chain adsorption process. Additionally, we find that the bulk polymer concentration at which the wetting transition in the poor solvent system occurs is not affected by the difference in surface–fluid interactions; however, a threshold value of surface–fluid interaction is needed to observe the wetting transition. We also find that with good solvent, increasing the chain length or the difference in the surface–polymer interaction relative to the surface–solvent interaction increases the surface coverage of polymer segments and independent chains for all surface curvatures. Finally, we demonstrate that the polymer segmental adsorption times are heavily influenced only by the surface–fluid interactions, although polymers desorb more quickly from highly curved surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1978

Delayed fracture of silicon: Silicon sheet growth development for the large area silicon sheet task of the low cost silicon solar array project

Bar specimens were cut from ingots of single crystal silicon, and acid etched prior to testing. Artificial surface flaws were introduced in specimens by indentation with a Knoop hardness tester. The specimens were loaded in four-point bending to 95 percent of the nominal fracture stress, while keeping the surface area, containing the flaw, wet with test liquids. No evidence of delayed fracture, and, therefore stress corrosion, of single crystal silicon was observed for liquid environments including water, acetone, and aqueous solutions of NaCl, NH4OH, and HNO3, when tested with a flaw parallel to a (110) surface. The fracture toughness was calculated.

Chen, T. J.↗

DOE OSTI2021

Amphilic Water-Lean Carbon Capture Solvent Wetting Behavior through Decomposition by Stainless-Steel Interfaces

In this work, we report on a combined experimental and theoretical study of the wetting and reactivity of water-lean carbon capture solvents on the surface of common column packing materials. Paradoxically, we find that these solvents are equally able to wet hydrophobic and hydrophilic surfaces. The solvents are amphiphilic and are able to adapt to any interfacial environment due to their inherent heterogeneous molecular structure. Ab initio molecular dynamics indicates that these structures enable the formation of a strong adlayer on the surface of hydrophilic surfaces like oxidized steel which promotes solvent decomposition akin to hydrolysis from surface oxides and hydroxides. This decomposition passivates the surface, making it effectively hydrophobic, and the decomposed solvent promotes leaching of the iron into the bulk fluid. This study links the wetting behavior to the observed corrosion of the steels via decomposition of solvent at steel interfaces. The overall affect is strongly dependent on the chemical composition of the solvent, in that amines are stable, whereas imines and alcohols are not. We also observed that plastic packing shows little to no solvent degradation, but an equal degree of wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the $\langle$101̅0$\rangle$ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl – species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl – passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO 2 hydrogenation activity. In conclusion, these findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Molecular Design of Supported MoO x Catalysts with Surface TaO x Promotion for Olefin Metathesis

A series of supported 3% MoOx catalysts were synthesized by incipient-wetness impregnation of 5%-15% TaO x surface modified γ-Al 2 O 3 support. The catalysts were characterized by in situ spectroscopies (DRIFTS, Raman, UV-vis, XAS) and multiple chemical probes (C 2 H 4 /C 4 H 8 titration, C 3 H 6 -TPSR, steady state propylene metathesis, NH 3 -IR adsorption). The supported tantalum oxide phase was present as surface TaO x sites on the γ-Al 2 O 3 support that capped that Al 2 O 3 surface hydroxyls. The change in available surface hydroxyls caused the subsequent anchoring of MoOx species to occur at different surface hydroxyls. This shifted the anchoring of MoO x species from basic (Al-OH) to neutral (Al 2 -OH) to more acidic (Al 3 -OH) surface hydroxyls as well as perturbation of the remaining alumina surface hydroxyls by the surface TaO x sites. The TaO x surface modified γ-Al 2 O 3 support increased the number of activated surface MoO x sites (Ns) by ~6x and the TOF by ~10x resulting in an increased activity of ~60x. In conclusion, It was found that the specific anchoring surface hydroxyls rather than the extent of oligomerization of the surface MoO x sites control the number of activated MoO x sites and TOF for propylene metathesis. No relationship between the nature of the surface Lewis/Brønsted acid sites and Ns and TOF were found to be present.

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NASA NTRS1999

Coupled Land Atmosphere Predictability

We have designed and executed a set of predictability experiments, designed around the driest and wettest June soil moisture anomalies from a CCM3 simulation forced by observed SST for the period from 1958 through 1998. Each set contains an ensemble of five runs, all begun on June I radiation date. One set of these experiments helps to assess the extent to which the wet or dry conditions depend solely on the initial state of the atmosphere. The other set of experiments helps to assess the extent to which the wet or dry conditions depend sole on the initial state of the land surface. Preliminary analysis of these experiments suggests that the initial atmospheric state is more important than the initial state of the surface soil moisture in predicting the occurrence of wet or dry periods. These results suggest that when the atmosphere is inclined to generate dry surface conditions (through reduced moisture availability and increased evaporation) it matters little what initial levels of soil water are at; the soil will rapidly dry out. The ensemble forcing the ensembles with dry soil conditions, but utilizing 'normal' atmospheric conditions show little if any indication of the sharp reduction in soil moisture experienced in the control, indicating that the 'normal' atmospheric state is more important than the initial state of the soil moisture in predicting the occurrence of drought. Our work to date has documented the response of surface hydrologic variability, particularly over North America, to atmospheric forcing. While we have seen some suggestion that pre-existing surface anomalies can affect atmospheric circulation over this region, by far the strongest signal is the atmospheric anomalies leading those of soil moisture and surface energy balance changes. This is not an unexpected result since wintertime NA precipitation links to remote atmospheric forcing by ENSO are known to be statistically significant. While warm season links to remote forcing are more tenuous and not well explored, the present results encourage us to examine in more detail the SST forcing from the tropical and North Pacific.

Roads, John↗

NASA NTRS2012

Impact of Land Model Calibration on Coupled Land-Atmosphere Prediction

Land-atmosphere (L-A) interactions play a critical role in determining the diurnal evolution of both planetary boundary layer (PBL) and land surface heat and moisture budgets, as well as controlling feedbacks with clouds and precipitation that lead to the persistence of dry and wet regimes. Recent efforts to quantify the strength of L-A coupling in prediction models have produced diagnostics that integrate across both the land and PBL components of the system. In this study, we examine the impact of improved specification of land surface states, anomalies, and fluxes on coupled WRF forecasts during the summers of extreme dry and wet land surface conditions in the U.S. Southern Great Plains. The improved land initialization and surface flux parameterizations are obtained through calibration of the Noah land surface model using the new optimization and uncertainty estimation subsystem in NASA's Land Information System (LIS-OPT/UE). The impact of the calibration on the a) spinup of the land surface used as initial conditions, and b) the simulated heat and moisture states and fluxes of the coupled WRF simulations is then assessed. Changes in ambient weather and land-atmosphere coupling are evaluated along with measures of uncertainty propagation into the forecasts. In addition, the sensitivity of this approach to the period of calibration (dry, wet, average) is investigated. Results indicate that the offline calibration leads to systematic improvements in land-PBL fluxes and near-surface temperature and humidity, and in the process provide guidance on the questions of what, how, and when to calibrate land surface models for coupled model prediction.

Santanello, Joseph A., Jr.↗

NASA NTRS2011

Impact of Conifer Forest Litter on Microwave Emission at L-Band

This study reports on the utilization of microwave modeling, together with ground truth, and L-band (1.4-GHz) brightness temperatures to investigate the passive microwave characteristics of a conifer forest floor. The microwave data were acquired over a natural Virginia Pine forest in Maryland by a ground-based microwave active/passive instrument system in 2008/2009. Ground measurements of the tree biophysical parameters and forest floor characteristics were obtained during the field campaign. The test site consisted of medium-sized evergreen conifers with an average height of 12 m and average diameters at breast height of 12.6 cm. The site is a typical pine forest site in that there is a surface layer of loose debris/needles and an organic transition layer above the mineral soil. In an effort to characterize and model the impact of the surface litter layer, an experiment was conducted on a day with wet soil conditions, which involved removal of the surface litter layer from one half of the test site while keeping the other half undisturbed. The observations showed detectable decrease in emissivity for both polarizations after the surface litter layer was removed. A first-order radiative transfer model of the forest stands including the multilayer nature of the forest floor in conjunction with the ground truth data are used to compute forest emission. The model calculations reproduced the major features of the experimental data over the entire duration, which included the effects of surface litter and ground moisture content on overall emission. Both theory and experimental results confirm that the litter layer increases the observed canopy brightness temperature and obscure the soil emission.

Kurum, Mehmet↗

NASA NTRS2016

Why Do Models Overestimate Surface Ozone in the Southeast United States?

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO(x) triple bond NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC(exp 4)RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25 deg x 0.3125 deg horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO(x) from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC(exp 4)RS observations of NO(x) and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NO(x) emissions from mobile and industrial sources must be reduced by 30-60%, dependent on the assumption of the contribution by soil NO(x) emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NO(x) emissions. We find that only half of isoprene oxidation proceeds by the high-NO(x) pathway to produce ozone; this fraction is only moderately sensitive to changes in NO(x) emissions because isoprene and NO(x) emissions are spatially segregated. GEOS-Chem with reduced NO(x) emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NO(x) oxidation products. However, the model is still biased high by 6 plus or minus 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Oxidation↗

DOE OSTI2021

Hydrogen Bonds and H 3 O + Formation at the Water Interface with Formic Acid Covered Anatase TiO 2

Carboxylic acid-modified TiO 2 surfaces in aqueous environment are of widespread interest, yet atomic-scale understanding of their structure is limited. In this work, we investigate formic acid (FA) on anatase TiO 2 (101) (A-101) in contact with water using density functional theory (DFT) and ab-initio molecular dynamics (AIMD). Isolated FA molecules adsorbed in a deprotonated bridging bidentate (BD) form on A-101 are found to remain stable at the interface with water, with the acid proton transferred to a surface oxygen to form a surface bridging hydroxyl (O br H). With increasing FA coverage, adsorbed monolayers of only BD and successively of alternating monodentate (MD) and BD species give rise to a higher concentration of surface O br H’s. Simulations of these adsorbed monolayers in water environment show that some protons are released from the surface O br H’s to water resulting in a negatively charged surface with nearby solvated H 3 O + ions. These results provide insight into the complex acid-base equilibrium between an oxide surface, adsorbates and water and can also help obtain a better understanding of the wetting properties of chemically modified TiO 2 surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗