Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Distinguishing different surface interactions for nucleotides adsorbed onto hematite and goethite particle surfaces through ATR-FTIR spectroscopy and DFT calculations.

Geochemical interfaces can impact the fate and transport of aqueous species in the environment including biomolecules. In this study, we investigate the surface chemistry of adsorbed nucleotides on two different minerals, hematite and goethite, using infrared spectroscopy and density functional theory (DFT) calculations. Attenuated total reflectance-Fourier transform infrared spectroscopy is used to probe the adsorption of deoxyadenosine monophosphate (dAMP), deoxyguanosine monophosphate (dGMP), deoxycytidine monophosphate (dCMP), and deoxythymidine monophosphate (dTMP) onto either hematite or goethite particle surfaces. The results show preferential adsorption of the phosphate group to either surface. Remarkably, surface adsorption of the four nucleotides onto either hematite or goethite have nearly identical experimental spectra in the phosphate region (900 to 1200 cm-1) for each mineral surface yet are distinctly different between the two minerals, suggesting differences in binding of these nucleotides to the two mineral surfaces. The experimental absorption frequencies in the phosphate region were compared to DFT calculations for nucleotides adsorbed through the phosphate group to binuclear clusters in either a monodentate or bidentate bridging coordination. Although the quality of the fits suggests that both binding modes may be present, the relative amounts differ on the two surfaces with preferential bonding suggested to be monodentate coordination on hematite and bidentate bridging on goethite. Possible reasons for these differences are discussed.

Connecting Thermodynamics of Alkali Ion Exchange on the Quartz (101) Surface with Density Functional Theory Calculations.

Periodic plane-wave density functional theory (DFT) calculations were performed on the α-quartz (SiO2) (101) surface to model exchange of adsorbed Li+ and either Na+, K+, or Rb+ in inner- and outer-sphere adsorbed, and aqueous configurations, which are charge-balanced with 2 Cl-. SiO- or SiOH groups represented the adsorption surface sites. The SiO- models included 58 H2O and 2 H3O+ molecules to approximate an aqueous environment, whereas the SiOH models had 59 H2O and 1 H3O+ molecules. The goal of this work is to calculate the heats of exchange for these alkali ions and to compare the results with those measured by flow microcalorimetry to ascertain the most probable mechanisms for these cations exchanging on the α-quartz (101) surface. Energy minimizations of each alkali ion adsorbed as outer-sphere complexes on SiOH surface sites, and as inner- and outer-sphere complexes on SiO- surface sites, were used to determine the energy of exchange (ΔEex) with Li+ for comparison with experimentally determined ΔHex values. Here, we present a novel method for calculating ΔEex using the difference in energies of geometry-optimized end member models. The aqueous and surface structures produced are similar to those observed experimentally. Although the trend for the calculated ΔEex values is consistent with those from the heats of exchange measured experimentally, the magnitude of our modeled ΔEex results is significantly larger than select experimental data from the literature [Peng, L. Zeta-Potentials and Enthalpy Changes in the Process of Electrostatic Self-Assembly of Cations on Silica Surface. Powder Technol. 2009, 193(1), 46-49]; we discuss the reasons for this discrepancy herein. The relative energy differences of the various configurations modeled have implications for the measurements of the surface charge via potentiometric titrations due to the more active role of alkali cations in quartz surface chemistry that have been previously considered as inert background electrolytes.

In Situ and Real-Time ATR-FTIR Temperature-Dependent Adsorption Kinetics Coupled with DFT Calculations of Dimethylarsinate and Arsenate on Hematite Nanoparticles.

Temperature-dependent kinetic studies of the adsorption of critical pollutants onto reactive components in soils and removal technologies provide invaluable rate information and mechanistic insight. Using attenuated total internal reflection Fourier transform infrared spectroscopy, we collected in situ spectra as a function of time, concentration, and temperature in the range of 5-50 °C (278-323 K) for the adsorption of arsenate (iAs) and dimethylarsinate (DMA) on hematite nanoparticles at pH 7. These experimental data were modeled with density functional theory (DFT) calculations on the energy barriers between surface complexes. The Langmuir adsorption kinetic model was used to extract values of the fast (<5 min) and slow (6-10 min) observed adsorption rate, initial rate constants of adsorption and desorption, Arrhenius parameters, effective activation energies (ΔEa), and pre-exponential factors (A). The trend in the kinetic parameters correlated with the type of surface complexes that iAs and DMA form, which are mostly bidentate binuclear compared to a mix of outer sphere and monodentate, respectively. The observed initial adsorption rates were found to be more sensitive to changes in the aqueous concentration of the arsenicals than slow rates. On average, iAs adsorbs 2.5× faster and desorbs 4× slower than dimethylarsinate (DMA). The ΔEa and A values for the adsorption of iAs bidentate complexes are statistically higher than those extracted for outer-sphere DMA by a factor of 3. The DFT results on adsorption energies and ΔEa barriers are consistent with the experimental data and provide a mechanistic explanation for the low ΔEa values observed. The presence of defect sites with under-coordinated Fe atoms or exchangeable surface water (i.e., Fe-OH2 groups) lowers activation barriers of adsorption. These results suggest that increasing organic substitutions on arsenate at the expense of As-O bonds decreases the effective energy barrier for complex formation and lowers the number of collisional orientations that result in binding to the hematite surface.

Adsorption of Organic Acids and Phosphate to an Iron (Oxyhydr)oxide Mineral: A Combined Experimental and Density Functional Theory Study.

The interaction of soil organic matter with mineral surfaces is a critical reaction involved in many ecosystem services, including stabilization of organic matter in the terrestrial carbon pool and bioavailability of plant nutrients. Using model organic acids typically present in soil solutions, this study couples laboratory adsorption studies with density functional theory (DFT) to provide physical insights into the nature of the chemical bonding between carboxylate functional groups and a model FeOOH cluster. Topological determination of electron density at bond critical points using quantum theory of atoms in molecules (QTAIM) analysis revealed that the presence of multiple bonding paths between the organic acid and the FeOOH cluster is essential in determining the competitive adsorption of organic acids and phosphate for FeOOH surface adsorption sites. The electron density and Laplacian parameter values from QTAIM indicated that the primary carboxylate-FeOOH bond was more ionic than covalent in nature. The experimental and computational results provide molecular-level evidence of the important role of electrostatic forces in the bonding between carboxylic acids and Fe-hydroxides. This knowledge may assist in the formulation of management studies to meet the challenges of maintaining ecosystems services in the face of a changing climate.

Evaluating Computational Chemistry Methods for Isotopic Fractionation between CO2(g) and H2O(g).

Quantum mechanical calculations can be useful in predicting equilibrium isotopic fractionations of geochemical reactions. However, these computational chemistry methods vary widely in their effectiveness in the prediction of various physical observables. Most studies employing the approach known as density functional theory (DFT) to model these observable quantities focus on predictive accuracy for energetics and geometries. In this study, several density functionals are evaluated against experimental bond lengths, harmonic vibrational frequencies, frequency shifts upon isotopic substitution, and 18O/16O isotopic fractionation between CO2(g) and H2O(g). Successful prediction of harmonic vibrational frequencies strongly correlates with successful prediction of isotopic fractionation, despite the possible introduction of errors by the harmonic approximation. Harmonic experimental frequencies, not anharmonic ones, must be used when comparing spectra and when predicting isotope fractionation. The B3LYP and X3LYP functionals perform more accurately in the evaluation of both harmonic vibrational frequencies and isotopic fractionation factors using the 6-311+G(d,p) and 6-311++G(2d,p) basis sets, achieving fractionation factor errors of 0.2-0.6‰ at 25 °C out of a total fractionation of 51‰. Error cancellation between vibrational frequencies and the harmonic approximation is crucial to their success. The above combination of exchange-correlation functionals and basis sets also well predicts the vibrational properties of interacting CO2 and H2O molecules, suggesting that they may be applicable to more complex geochemical reactions involving C and O isotopic fractionations.

Gibbsite (100) and Kaolinite (100) Sorption of Cadmium(II): A Density Functional Theory and XANES Study of Structures and Energies.

Due to the potential toxicity of cadmium (Cd2+) and its presence in various waste products found in the environment, it is necessary to develop methods to attenuate and remediate Cd2+ waste. Sorption of Cd2+ to mineral surfaces is a potential route to accomplish this goal. This work focused on improving our molecular-scale understanding of the chemistry of Cd2+ interactions with gibbsite and kaolinite mineral surfaces. Plane-wave density functional theory (DFT) energy minimization calculations and molecular dynamics simulations were used to study the adsorption energies and the nature of the bonds between Cd2+ and the mineral surfaces for possible inner- and outer-sphere surface complexes. Models resulting from the DFT calculations were used to calculate theoretical XANES spectra that were compared with experimental Cd LIII XANES of aqueous Cd2+ as a proxy for outer-sphere Cd2+ hydrated complexes associated with the mineral surfaces. These studies suggest that Cd2+ would favorably bond to the (100) surfaces of both kaolinite and gibbsite through a bidentate mononuclear interaction. However, the results indicate that mixtures of surface complexes on these minerals are likely.

Density functional theory modeling of chromate adsorption onto ferrihydrite nanoparticles.

Density functional theory (DFT) calculations were performed on a model of a ferrihydrite nanoparticle interacting with chromate ([Formula: see text]) in water. Two configurations each of monodentate and bidentate adsorbed chromate as well as an outer-sphere and a dissolved bichromate ([Formula: see text]) were simulated. In addition to the 3-D periodic planewave DFT models, molecular clusters were extracted from the energy-minimized structures. Calculated interatomic distances from the periodic and cluster models compare favorably with Extended X-ray Absorption Fine Structure spectroscopy values, with larger discrepancies seen for the clusters due to over-relaxation of the model substrate. Relative potential energies were derived from the periodic models and Gibbs free energies from the cluster models. A key result is that the bidentate binuclear configuration is the lowest in potential energy in the periodic models followed by the outer-sphere complex. This result is consistent with observations of the predominance of bidentate chromate adsorption on ferrihydrite under conditions of high surface coverage (Johnston Environ Sci Technol 46:5851-5858, 2012). Cluster models were also used to perform frequency analyses for comparison with observed ATR FTIR spectra. Calculated frequencies on monodentate, bidentate binuclear, and outer-sphere complexes each have infrared (IR)-active modes consistent with experiment. Inconsistencies between the thermodynamic predictions and the IR-frequency analysis suggest that the 3-D periodic models are not capturing key components of the system that influence the adsorption equilibria under varying conditions of pH, ionic strength and electrolyte composition. Model equilibration via molecular dynamics (MD) simulations is necessary to escape metastable states created during DFT energy minimizations based on the initial classical force field MD-derived starting configurations.

Effect of Ions on H-Bond Structure and Dynamics at the Quartz(101)-Water Interface.

We use ab initio molecular dynamics simulations to study the effect of ions on the structure and dynamics of the quartz(101)-water interface. We study several IA (Na+, Rb+) and IIA (Mg2+, Sr2+) cations, with Cl- as counterion, adsorbed onto acidic, neutral, and basic surface configurations at 300 and 373 K. We find that both cations and anions can bond directly to the surface and perturb the local H-bond network. The adsorbed ions promote the formation of intrasurface H-bonds, as shown by vibrational density of states and orientations of the surface silanols. Both local and global structural correlations of the interfacial H-bond network are studied using a structural definition of the H-bond and a network correlation function. We find the ions' effect on the solvent structure exhibits a complex dependence on specific surface interactions. The structure-making properties of ions are enhanced at the quartz surface, particularly for ions adsorbed without a complete hydration shell, and the structuring effect extends beyond the first solvation shell. The ions have a lesser effect on solvent structure in solution, especially in the presence of counterions. In fact, cations that are the greatest "structure makers" at the surface are the greatest "structure breakers" when in solution with a counterion. Therefore, we find the ions cannot be simply classified as "structure making" or "structure breaking". We discuss the implications of these findings for the effect of ions on the dissolution rate, surface charge, and solvent structure.

Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iß, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iß allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of bacterial, algal, and animal cellulose, interacts with hemicellulose, is poorly hydrated, and is targeted by the protein expansin during wall loosening. To obtain information about the C6 hydroxymethyl conformation of these plant celluloses, we carried out DFT calculations of (13)C chemical shifts, using the Iα and Iß crystal structures as templates and varying the C5-C6 torsion angle. Comparison with the experimental chemical shifts suggests that all interior cellulose favor the tg conformation, but cellulose d also has a similar propensity to adopt the gt conformation. These results indicate that cellulose in plant primary cell walls, due to their interactions with matrix polysaccharides, and has polymorphic structures that are not a simple superposition of the Iα and Iß allomorphs, thus distinguishing them from bacterial and animal celluloses.

X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces.

Sulfate adsorption on mineral surfaces is an important environmental chemical process, but the structures and respective contribution of different adsorption complexes under various environmental conditions are unclear. By combining sulfur K-edge XANES and EXAFS spectroscopy, quantum chemical calculations, and surface complexation modeling (SCM), we have shown that sulfate forms both outer-sphere complexes and bidentate-binuclear inner-sphere complexes on ferrihydrite surfaces. The relative fractions of the complexes vary with pH, ionic strength (I), and sample hydration degree (wet versus air-dried), but their structures remained the same. The inner-sphere complex adsorption loading decreases with increasing pH while remaining unchanged with I. At both I = 0.02 and 0.1 M, the outer-sphere complex loading reaches maximum at pH ∼5 and then decreases with pH, whereas it monotonically decreases with pH at I = 0.5 M. These observations result from a combination of the ionic-strength effect, the pH dependence of anion adsorption, and the competition between inner- and outer-sphere complexation. Air-drying drastically converts the outer-sphere complexes to the inner-sphere complexes. The respective contributions to the overall adsorption loading of the two complexes were directly modeled with the extended triple layer SCM by implementing the bidentate-binuclear inner-sphere complexation identified in the present study. These findings improve our understanding of sulfate adsorption and its effects on other environmental chemical processes and have important implications for generalizing the adsorption behavior of anions forming both inner- and outer-sphere complexes on mineral surfaces.

Competitive Adsorption of Acetic Acid and Water on Kaolinite.

Mineral dust is prevalent in the atmosphere as a result of emissions from natural and anthropogenic sources. As mineral dust particles undergo long-distance transport, they are exposed to trace gases and water vapor. We have characterized the interactions of acetic acid on kaolinite using diffuse reflectance infrared Fourier transform spectroscopy and molecular modeling to determine the chemisorbed species present. After the addition of acetic acid, gas-phase water was introduced to explore how water vapor competes with acetic acid for surface sites. We found that four chemisorbed acetate species are present on kaolinite after exposure to acetic acid in which acetate bonds through a monodentate, bidenatate, or bidentate bridging linkage with an aluminum atom. These species exhibit varying levels of stability after the introduction of water, indicating that water vapor affects the adsorption of organic acids. These results indicate that the type of chemisorbed species determines its stability toward competitive adsorption, which has potential implications for atmospheric composition and ice nucleation.

Tertiary model of a plant cellulose synthase.

A 3D atomistic model of a plant cellulose synthase (CESA) has remained elusive despite over forty years of experimental effort. Here, we report a computationally predicted 3D structure of 506 amino acids of cotton CESA within the cytosolic region. Comparison of the predicted plant CESA structure with the solved structure of a bacterial cellulose-synthesizing protein validates the overall fold of the modeled glycosyltransferase (GT) domain. The coaligned plant and bacterial GT domains share a six-stranded ß-sheet, five α-helices, and conserved motifs similar to those required for catalysis in other GT-2 glycosyltransferases. Extending beyond the cross-kingdom similarities related to cellulose polymerization, the predicted structure of cotton CESA reveals that plant-specific modules (plant-conserved region and class-specific region) fold into distinct subdomains on the periphery of the catalytic region. Computational results support the importance of the plant-conserved region and/or class-specific region in CESA oligomerization to form the multimeric cellulose-synthesis complexes that are characteristic of plants. Relatively high sequence conservation between plant CESAs allowed mapping of known mutations and two previously undescribed mutations that perturb cellulose synthesis in Arabidopsis thaliana to their analogous positions in the modeled structure. Most of these mutation sites are near the predicted catalytic region, and the confluence of other mutation sites supports the existence of previously undefined functional nodes within the catalytic core of CESA. Overall, the predicted tertiary structure provides a platform for the biochemical engineering of plant CESAs.

Experimental study of strontium adsorption on anatase nanoparticles as a function of size with a density functional theory and CD model interpretation.

The effect of particle size on the adsorption of Sr(2+) onto monodisperse nanometer diameter (4, 20, and 40 nm) anatase samples has been evaluated quantitatively with macroscopic experimental studies. The adsorption of Sr(2+) onto the anatase particles was evaluated by potentiometric titrations in NaCl media, at two ionic strengths (0.03 and 0.3 m), and over a wide range of pH (3-11) and surface loadings, at a temperature of 25 °C. Adsorption of Sr(2+) to the surface of the 20 and 40 nm diameter samples was similar, whereas the Sr(2+) adsorption titration curves were shallower for the 4 nm diameter samples. At high pH, the smallest particles adsorbed slightly less Sr(2+) than was adsorbed by the larger particles. At the molecular scale, density functional theory (DFT) calculations were used to evaluate the most stable Sr(2+) surface species on the (101) anatase surface (the predominant crystal face). An inner-sphere Sr-tridentate surface species was found to be the most stable. The experimental data were described with a charge distribution (CD) and multisite complexation (MUSIC) model, with a Basic Stern layer description of the electric double layer. The resulting surface complexation model explicitly incorporated the molecular-scale information from the DFT simulation results. For 20 and 40 nm diameter anatase, the CD value for the Sr-tridentate species was calculated using a bond valence interpretation of the DFT-optimized geometry. The CD value for the 4 nm sample was smaller than that for the 20 and 40 nm samples, reflecting the shallower Sr(2+) adsorption titration curves. The adsorption differences between the smallest and larger anatase particles can be rationalized by water being more highly structured near the 4 nm anatase sample and/or the Sr-tridentate surface species may require more well-developed surface terraces than are present on the 4 nm particles.

Plagioclase dissolution during CO2-SO2 cosequestration: effects of sulfate.

Geologic CO2 sequestration (GCS) is one of the most promising methods to mitigate the adverse impacts of global climate change. The performance of GCS can be affected by mineral dissolution and precipitation induced by injected CO2. Cosequestration with acidic gas such as SO2 can reduce the high cost of GCS, but it will increase the sulfate's concentration in GCS sites, where sulfate can potentially affect plagioclase dissolution/precipitation. This work investigated the effects of 0.05 M sulfate on plagioclase (anorthite) dissolution and subsequent mineral precipitation at 90 °C, 100 atm CO2, and 1 M NaCl, conditions relevant to GCS sites. The adsorption of sulfate on anorthite, a Ca-rich plagioclase, was examined using attenuated total reflectance Fourier-transform infrared spectroscopy and then simulated using density functional theory calculations. We found that the dissolution rate of anorthite was enhanced by a factor of 1.36 by the formation of inner-sphere monodentate complexes between sulfate and the aluminum sites on anorthite surfaces. However, this effect was almost completely suppressed in the presence of 0.01 M oxalate, an organic ligand that can exist in GCS sites. Interestingly, sulfate also inhibited the formation of secondary mineral precipitation through the formation of aluminum-sulfate complexes in the aqueous phase. This work, for the first time, reports the surface complexation between sulfate and plagioclase that can occur in GCS sites. The results provide new insights for obtaining scientific guidelines for the proper amount of SO2 coinjection and finally for evaluating the economic efficiency and environmental safety of GCS operations.

A multi-scale assessment of the impact of salinity on the desorption of chromate from hematite: Sea level rise implications.

The solubility and transport of Cr(VI) is primarily controlled by adsorption-desorption reactions at the surfaces of soil minerals such as iron oxides. Environmental properties such as pH, ionic strength, and ion competition are expected to affect the mobility and fate of Cr(VI). Sea level rise (SLR), and consequent seawater intrusion, is creating a new biogeochemical soil environment at coastal margins, potentially impacting Cr(VI) retention at contaminated sites. We employed in-situ ATR-FTIR spectroscopy and DFT calculations to investigate at the molecular level the adsorption of Cr(VI) on the hematite surface and its desorption by sulfate, as a function of pH and ionic strength. We further used a batch experiment to assess Cr(VI) desorption at varying artificial seawater (ASW) concentrations. IR results demonstrate the complexity of Cr(VI) adsorption, showing a combination of monodentate inner-sphere complexation at high pH and dichromate outer-sphere (∼75%) at low pH. The Cr(VI)-complexes exhibited desorption induced by increasing pH values (58% of desorption) and sulfate competition (∼40% desorption). ASW desorbed ∼20% more Cr(VI), even at just 1% concentration. Our findings provide insight into Cr(VI)-adsorption complexation that controls the retention and remobilization of Cr(VI) on Fe-oxide minerals. The results point to an elevated risk of Cr(VI) mobilization in contaminated soils affected by SLR.

Bridging molecular-scale interfacial science with continuum-scale models.

Solid-water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid-water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions.

Anatase nanoparticle surface reactivity in NaCl media: a CD-MUSIC model interpretation of combined experimental and density functional theory studies.

The effect of particle size on the primary charging behavior of a suite of monodisperse nanometer diameter (4, 20, and 40 nm) anatase samples has been quantitatively examined with macroscopic experimental studies. The experimental results were evaluated using surface complexation modeling, which explicitly incorporated corresponding molecular-scale information from density functional theory (DFT) simulation studies. Potentiometric titrations were completed in NaCl media, at five ionic strengths (from 0.005 to 0.3 m), and over a wide pH range (3-11), at a temperature of 25 °C. From the experimental results, the pH of zero net proton charge (pHznpc) for the 4 and 20 nm diameter samples was 6.42, whereas the pHznpc was 6.22 for the 40 nm sample. The slopes of the net proton charge curves increased with an increase in particle size. Multisite surface complexation and charge distribution (CD) models, with a Basic Stern layer description of the electric double layer, were developed to describe all experimental data. Fits to the experimental data included an inner-sphere Na-bidentate species, an outer-sphere Na-monodentate species, and outer-sphere Cl-monodentate species. DFT simulations found the Na-bidentate species to be the most stable species on the (101) anatase surface (the predominant crystal face). The CD value for the Na-bidentate species was calculated using a bond valence interpretation of the DFT-optimized geometry. The Stern layer capacitance value varied systematically with particle size. The collective experimental and modeling studies show that subtle differences exist in the interface reactivity of nanometer diameter anatase samples. These results should help to further elucidate an understanding of the solid-aqueous solution interface reactivity of nanosized particles.

Development of a ReaxFF reactive force field for titanium dioxide/water systems.

A new ReaxFF reactive force field has been developed to describe reactions in the Ti-O-H system. The ReaxFF force field parameters have been fitted to a quantum mechanical (QM) training set containing structures and energies related to bond dissociation energies, angle and dihedral distortions, and reactions between water and titanium dioxide, as well as experimental crystal structures, heats of formation, and bulk modulus data. Model configurations for the training set were based on DFT calculations on molecular clusters and periodic systems (both bulk crystals and surfaces). ReaxFF reproduces accurately the QM training set for structures and energetics of small clusters. ReaxFF also describes the relative energetics for rutile, brookite, and anatase. The results of ReaxFF match reasonably well with those of QM for water binding energies, surface energies, and H2O dissociation energy barriers. To validate this ReaxFF description, we have compared its performance against DFT/MD simulations for 1 and 3 monolayers of water interacting with a rutile (110) surface. We found agreement within a 10% error between the DFT/MD and ReaxFF water dissociation levels for both coverages.

Identification and characterization of a cellulose binding heptapeptide revealed by phage display.

Cellulose nanowhiskers (CNWs) were used in conjunction with phage display technology to identify polypeptides which bind the crystalline region of cellulose. A consensus peptide WHWTYYW was identified to efficiently bind the CNWs. The binding affinities of specific phage particles were assessed using biopanning assays and enzyme-linked immunosorbent assay (ELISA). The WHWTYYW peptide was synthesized and isothermal titration calorimetry (ITC) analysis showed that the peptide exhibited a binding constant of ∼10(5) M(-1) toward the crystalline CNWs. In order to understand how the affinity of this peptide differs for noncrystalline cellulose, binding properties were characterized using cello-oligosaccharides as substrates. Binding analysis was performed using UV spectroscopy and fluorescence quenching experiments. The specific molecular interactions of the WHWTYYW peptide with cellohexaose were examined using nuclear magnetic resonance (NMR). Interactions of this peptide with crystalline cellulose were also investigated using classical molecular modeling and quantum mechanical calculations of (13)C NMR chemical shifts. The NMR experiments and calculations indicate that the WHWTYYW peptide exhibits a bent structure when bound, allowing the Y5 amino acid to form a CH/π stacking interaction and H-bond with the glucose ring of cellulose.