Dissociative Adsorption Of Water Research Articles

Work function and electrochemistry of ZnO (wurtzite) single crystals (F-1:L07)

The work functions of two polar surfaces of ZnO (wurtzite), i.e., O-(000–1) and Zn-(0001) are determined by photoelectron spectroscopy in ultrahigh vacuum or in the presence of oxygen or water vapor at near-ambient pressures, and by Kelvin probe in air. The work functions were also determined by Mott-Schottky analysis in aqueous or aprotic (acetonitrile) electrolyte solutions. The values obtained by different techniques and in different environments are much less scattered compared to the fluctuations, reported for TiO2 (anatase or rutile). The Zn-(0001) surface has a smaller work function for all the solid/vacuum and solid/gas interfaces, and also in the acetonitrile electrolyte solution. Solely at the aqueous electrochemical interface, the difference is small or even opposite. We propose a hypothesis that the dissociative water adsorption on the O-(000–1) is responsible for this irregular downshift of the work function in aqueous medium.

Water adsorption on ferroelectric PbTiO3 (0 0 1) surface: A density functional theory study

In this work, combining the density functional theory (DFT) calculations and the ab initio molecular dynamics (AIMD) simulations, the water adsorption behavior, including the molecular and the dissociative adsorption on the negatively polarized (0 0 1) surface of ferroelectric PbTiO3 was comprehensively studied. Our theoretical results show that the dissociative adsorption of water is more energetically favorable than the molecular adsorption on the pristine PbTiO3 (0 0 1) surface. It has been also found that introducing surface oxygen vacancies (OV) can enhance the thermodynamic stability of dissociative adsorption of water molecule. The AIMD simulations demonstrate that water molecule can spontaneously dissociate into hydrogen atoms (H) and hydroxyl groups (OH) on the pristine PbTiO3 (0 0 1) surface at room temperature. Moreover, the surface OV can effectively facilitate the dissociative adsorption of water molecules, leading to a high surface coverage of OH group, thus giving rise to a high reactivity for water splitting on defective PbTiO3 (0 0 1) surface with OV. Our results not only comprehensively understand the reason for the photocatalytic water oxidation activity of single domain PbTiO3, but also shed light on the development of high performance ferroelectric photocatalysts for water splitting.

(Invited) Development of Multifunctional Nanoscale Reactors for Electrocatalytic Oxidation of Dimethyl Ether Fuel

There has been growing interest in utilizing small (simple) organic molecules, as alternative fuels to hydrogen, for electrochemical energy conversion in fuel cells. Dimethyl ether (DME) is one of the possible choices in this respect. But electrooxidation of DME is rather slow at ambient conditions. Obviously, there is a need to develop novel electrocatalytic materials.Bimetallic PtSn catalysts were found to be almost as active as PtRu for methanol oxidation, and PtSn was even more efficient toward the electrooxidation of ethanol where breaking of C-C bond is required. While PtRu forms a single-phase homogeneous (intermetallic) alloy in which Ru is largely metallic, tin does not maintain its metallic state in PtSn (heterogenous alloy) and is transformed readily to such oxygenated species as Sn oxides or hydroxides. During operation of PtSn, the Pt component retains its mostly metallic character and act independently as Pt0 catalyst. By analogy to Ru, the Sn “bifunctional agent” tends to activate the water dissociative adsorption and increases population of chemisorbed hydroxyl groups to diminish the Pt-poisoning effect through enhanced oxidation of CO-type intermediates. Nevertheless, the DME oxidation on both PtRu or PtSn is still kinetically less favorable, relative to the systems’ performance toward methanol. While Sn, and particularly Ru alloyed atoms activate readily the water dissociative adsorption on Pt and permit the oxidative stripping of the poisoning CO-type adsorbates, the feasibility of the enhancement of the of the DME adsorption and activation through alteration of the electronic structure of Pt catalytic sites has not been fully explained. By analogy to the ethanol oxidation, Pt sites in the heterogeneous PtSn alloy are active toward dissociation of the DME molecule but the Sn additive is less efficient than Ru (from intermetallic PtRu) in the oxidative removal of poisoning adsorbates. But PtRu is probably the most active during oxidation of methanol, and this small organic molecule is also the DME-oxidation-reaction intermediate. Nevertheless, in comparison to bare Pt, electrooxidation of DME starts at PtRu and PtSn at less positive potentials.We pursue a concept of utilization of multicomponent hybrid electrocatalytic systems or nanoreactors utilizing zirconia oxide matrices for supporting and activation of primarily PtSn nanoparticles supported onto Vulcan XC-72 carbon black carriers. Electrocatalytic activity of Vulcan-supported PtSn (PtSn/V) nanostructured alloys supported onto ZrO2 matrices has been significantly enhanced toward electrooxidation of DME in acid medium (0.5 mol dm-3 H2SO4) by decorating PtSn/V with bimetallic PtRu nanoparticles. The enhancement effect concerns both shifting the onset potential for the DME-oxidation toward less positive values and increase of the DME electrocatalytic current densities recorded under both cyclic voltammetric and chronoamperometric conditions. The activating capabilities of ruthenium nanostructures seem to originate from the existence (even below 0.45 V vs. RHE) of reactive ruthenium oxo/ hydroxo groups on their surfaces capable of inducing the oxidative removal of poisoning (CO-type) adsorbates from the neighboring platinum catalytic sites. In this respect, the Ru-oxo species seem to support activity of Sn forming with Pt the PtSn heterogenous alloy. The PtSn/V admixed with PtRu decorated ZrO2 exhibit very high activity toward the oxidation of methanol which is also an important DME-oxidation intermediate. On the whole, the hybrid materials composed of Vulcan-supported PtSn decorated with Ru or PtRu nanoparticles decorated zirconia oxide seem to act as multifunctional nanoreactors inducing not only stripping of poisoning adsorbates but also catalyzing oxidation of the DME-reaction intermediates (methanol). Acknowledgement Authors acknowledge financial support of the National Science Center (Poland) under Opus Project 2018/29/B/ST5/02627.

Diverse Hierarchical Meso/Nanoporous Pt Film Electrocatalysts Prepared via Hydrogen Adsorption-Assisted Dynamic Soft Templating.

In this study, we present an innovative approach for creating hierarchical meso/nanoporous Pt films using dynamic soft templating. The fabrication process, called dynamic soft templating, involves Pt electrodeposition within a specialized bicontinuous microemulsion (BME) system characterized by a sophisticated three-dimensional network comprising water and oil phases, surfactants, and cosurfactants. Pt electrodeposition exclusively occurs in the water phase of the BME. This results in a porous Pt film exhibiting a nanostructure mirroring the oil solution/water solution nanostructure (solution/solution structure) of the BME, the size of which can be tailored by adjusting the BME composition. Through a simultaneous interplay of Pt electrodeposition and overpotential deposition of hydrogen (H-OPD, dissociative adsorption of water), potential-dependent Pt mesostructures are dynamically shaped. As a result, we achieve diverse morphologies in the form of hierarchical meso/nanoporous Pt films. The potential applications of the films are evaluated as electrocatalysts for the methanol oxidation reaction (MOR), and it was found that the electrocatalytic performances seem to be sensitive to nanoporosity and not relevant to mesoporosity.

Effect of water vapor on low temperature SCR performances over Cu and Mn-based catalysts: A comparison study

In this study, the commonly used Cu or Mn-based low-temperature SCR catalysts were employed to investigate their different reaction behaviors in the presence of high-content water vapor. Experimental results reveal that CuCeTi sample possesses superior water resistance at low temperature compared with MnCeTi catalyst. Upon the introduction of water vapor, both catalysts exhibit a quick loss in deNOx efficiency, while that is more pronounced on MnCeTi sample. In addition, unlike CuCeTi sample, MnCeTi catalyst also shows a gradual deactivation tendency after initial quick activity loss. Characterization and simulation results indicate that H2O is more easily adsorbed and dissociated on MnCeTi catalyst, showing stronger suppression on NH3 adsorption, causing more serious initial deactivation. Furthermore, more abundant hydroxyl groups derived from dissociative adsorption of water on MnCeTi catalyst will lead to more NH4NO3 deposition and the decrease in redox capacity. This is the main reason of gradual deactivation of MnCeTi catalyst at high-content water vapor. Such findings could pave a new way for development of highly efficient SCR catalysts with good water resistance for real application.

Gas-Phase Production of Hydroxylated Silicon Oxide Cluster Cations: Structure, Infrared Spectroscopy, and Astronomical Relevance.

The interaction of free cationic silicon oxide clusters, Si x O y + (x = 2-5, y ≥ x), with dilute water vapor, was investigated in a flow tube reactor. Product mass distributions indicate cluster size-dependent dissociative water adsorption. To probe the structure and vibrational spectra of the resulting Si x O y H2 + (x = 2-4) clusters, we employed infrared multiple photon dissociation spectroscopy and density functional theory calculations. The planar rhombic cluster core of the disilicon oxides (x = 2) appears to be retained upon dissociative adsorption of one H2O unit, whereas a significant structural transformation of the tri- and tetra-silicon oxides (x = 3 and 4) is induced, resulting in an increased coordination of the Si atoms and more 3D cluster structures. In an astronomical context, we discuss the potential relevance of Si x O y H z + clusters as seeds for dust nucleation and catalysts for carbon-based chemistry in diffuse or translucent interstellar clouds, where all the necessary conditions for producing these species are found. In the produced clusters, the frequency of the isolated silanol Si-OH stretching vibrational mode is considerably blue-shifted compared to that in hydroxylated bulk silica and small inorganic compounds. This mode has a characteristic frequency range between 1200 cm-1 (8.3 μm) and 1090 cm-1 (9.2 μm) and is associated with the anomalously small Si-OH bond lengths in these ionised species. In infrared observations such high frequency Si-O stretching modes are usually associated with a pure bulk silica component of silicate cosmic dust. The presence of Si x O y H2 + clusters in low silica astrophysical environments could thus potentially be detected via their signature Si-O band using the James Webb space telescope.

Atomic structure and water arrangement on K-feldspar microcline (001).

The properties of clouds, such as their reflectivity or their likelihood to precipitate, depend on whether the cloud droplets are liquid or frozen. Thus, understanding the ice nucleation mechanisms is essential for the development of reliable climate models. Most ice nucleation in the atmosphere is heterogeneous, i.e., caused by ice nucleating particles such as mineral dusts or organic aerosols. In this regard, K-feldspar minerals have attracted great interest recently as they have been identified as one of the most important ice nucleating particles under mixed-phase cloud conditions. The mechanism by which feldspar minerals facilitate ice nucleation remains, however, elusive. Here, we present atomic force microscopy (AFM) experiments on microcline (001) performed in an ultrahigh vacuum and at the solid-water interface together with density functional theory (DFT) and molecular dynamics (MD) calculations. Our ultrahigh vacuum data reveal features consistent with a hydroxyl-terminated surface. This finding suggests that water in the residual gas readily reacts with the surface. Indeed, the corresponding DFT calculations confirm a dissociative water adsorption. Three-dimensional AFM measurements performed at the mineral-water interface unravel a layered hydration structure with two features per surface unit cell. A comparison with MD calculations suggests that the structure observed in AFM corresponds to the second hydration layer rather than the first water layer. In agreement with previous computation results, no ice-like structure is seen, questioning an explanation of the ice nucleation ability by lattice match. Our results provide an atomic-scale benchmark for the clean and water-covered microcline (001) plane, which is mandatory for understanding the ice nucleation mechanism on feldspar minerals.

Theoretical insights into the effect of surface structure and anion ordering on the properties of SrTaO2N for photocatalytic water splitting

AbstractAs one of the representative perovskite‐type oxynitride photocatalysts, SrTaO2N has the ability to split water in the visible‐light region. It was found that the surface modification and interfacial design of SrTaO2N‐based materials are closely related to the photocatalytic activity, but the microscopic mechanisms of these experimental phenomena are not well understood. In this work, we have utilized density functional theory (DFT) calculations to investigate the effect of anion ordering and exposed terminations on the electronic structures, optical absorption, water adsorption and the mechanisms of water oxidation and reduction reactions of SrTaO2N. Our results indicate that cis configurations are more stable than trans configurations. The anion ordering has an important effect on the band gap and optical absorption coefficient. The terminations with exposed Ta atoms are more stable and have bigger work functions than those with exposed Sr atoms possibly due to the bonding ionicity and surface dipoles. The dissociative adsorption of water is energetically more favorable than the molecular adsorption on most surfaces. The highly active sites of hydrogen evolution reaction (HER) are the exposed nonmetal atoms. Terminations with exposed Sr and N atoms have lower overpotentials (0.70–0.77 V) of oxygen evolution reaction (OER) than others. They are comparable to the calculated results of common photocatalysts, such as Co3O4 and TiO2. This study sheds light on the relationship between the termination structure with different anion orders and the photocatalysis‐related properties of SrTaO2N at a molecular level, which provides guidance for constructing highly active photocatalytic materials.

Molecular and Dissociative Adsorption of H2O on ZrO2/YSZ Surfaces

The work involves first-principles calculations to study the mechanism of adsorption of water molecules on the surface of ZrO2 and their yttrium-stabilized structures (YSZ). Calculations of the electronic properties of ZrO2 showed that during the m-t phase transformation of ZrO2, the Fermi level first shifts by 0.125 eV towards the conduction band, and then in the t-c region goes down by 0.08 eV. In this case, the band gaps for c-ZrO2, t-ZrO2 and m-ZrO2, respectively, are 5.140 eV, 5.898 eV and 5.288 eV. Calculations to determine the surface energy showed that t-ZrO2 (101) and m-ZrO2 (111) have the most stable structure, on the basis of which it was first discovered that the surface energy is somehow inversely related to the value of the band gap, since as the band gap increases, the surface energy tends to decrease. An analysis of the mechanism of water adsorption on the surface of t-ZrO2 (101) and t-YSZ (101) showed that H2O on unstabilized t-ZrO2 (101) is adsorbed dissociatively with an energy of −1.22 eV, as well as by the method of molecular chemisorption with an energy of −0.69 eV and the formation of a hydrogen bond with a bond length of 1.01 Å. In the case of t-YSZ (101), water is molecularly adsorbed onto the surface with an energy of −1.84 eV. Dissociative adsorption of water occurs at an energy of −1.23 eV, near the yttrium atom. The obtained results complement the database of research works carried out in the field of the application of biocompatible zirconium dioxide crystals and ceramics in green energy generation, and can be used in designing humidity-to-electricity converters and in creating solid oxide fuel cells based on ZrO2.

Accurate descriptions of molecule-surface interactions for understanding CO2 capture by MgO-based sorbents in wet conditions

MgO shows promise as a CO2 sorbent material for the intermediate temperature range. Here, a hybrid computation scheme, xDH:GGA that combines the XYG3-type of doubly hybrid (xDH) and the generalized gradient approximation (GGA) functionals, is applied. It aims to provide an accurate description of molecular-surface interactions to reduce calculation uncertainties in exploring CO2 capture mechanisms for MgO-based systems. After validating the accuracy of the hybrid scheme by modeling CO adsorption on both MgO(100) and NaCl(100) surfaces against the experimental results, CO2 capture in wet conditions is examined. The results highlight the importance of competitive adsorption between CO2 and water, which undermines the significance of the conventionally identified active sites on MgO surfaces. In contrast, the intermediate Mg(OH)2 layer emerges as a more viable active phase, whose presence was experimentally observed, where the layered structure of Mg(OH)2 is found to kinetically retard water dissociative adsorption. In addition to surface areas and pore structures, our study emphasizes the pivotal role played by selective CO2 chemical adsorption in the development of effective CO2 sorbent materials.

A Detailed Comparative Analysis of the Structural Stability and Electron-Phonon Properties of ZrO2: Mechanisms of Water Adsorption on t-ZrO2 (101) and t-YSZ (101) Surfaces.

In this study, we considered the structural stability, electronic properties, and phonon dispersion of the cubic (c-ZrO2), tetragonal (t-ZrO2), and monoclinic (m-ZrO2) phases of ZrO2. We found that the monoclinic phase of zirconium dioxide is the most stable among the three phases in terms of total energy, lowest enthalpy, highest entropy, and other thermodynamic properties. The smallest negative modes were found for m-ZrO2. Our analysis of the electronic properties showed that during the m-t phase transformation of ZrO2, the Fermi level first shifts by 0.125 eV toward higher energies, and then decreases by 0.08 eV in the t-c cross-section. The band gaps for c-ZrO2, t-ZrO2, and m-ZrO2 are 5.140 eV, 5.898 eV, and 5.288 eV, respectively. Calculations based on the analysis of the influence of doping 3.23, 6.67, 10.35, and 16.15 mol. %Y2O3 onto the m-ZrO2 structure showed that the enthalpy of m-YSZ decreases linearly, which accompanies the further stabilization of monoclinic ZrO2 and an increase in its defectiveness. A doping-induced and concentration-dependent phase transition in ZrO2 under the influence of Y2O3 was discovered, due to which the position of the Fermi level changes and the energy gap decreases. It has been established that the main contribution to the formation of the conduction band is made by the p-states of electrons, not only for pure systems, but also those doped with Y2O3. The t-ZrO2 (101) and t-YSZ (101) surface models were selected as optimal surfaces for water adsorption based on a comparison of their surface energies. An analysis of the mechanism of water adsorption on the surface of t-ZrO2 (101) and t-YSZ (101) showed that H2O on unstabilized t-ZrO2 (101) is adsorbed dissociatively with an energy of -1.22 eV, as well as by the method of molecular chemisorption with an energy of -0.69 eV and the formation of a hydrogen bond with a bond length of 1.01 Å. In the case of t-YSZ (101), water is molecularly adsorbed onto the surface with an energy of -1.84 eV. Dissociative adsorption of water occurs at an energy of -1.23 eV, near the yttrium atom. The results show that ab initio approaches are able to describe the mechanism of doping-induced phase transitions in (ZrO2+Y2O3)-like systems, based on which it can be assumed that DFT calculations can also flawlessly evaluate other physical and chemical properties of YSZ, which have not yet been studied quantum chemical research. The obtained results complement the database of research works carried out in the field of the application of biocompatible zirconium dioxide crystals and ceramics in green energy generation, and can be used in designing humidity-to-electricity converters and in creating solid oxide fuel cells based on ZrO2.

Mathematical Modeling of Alkaline Direct Glycerol Fuel Cells

Mathematical modeling and computer simulation are tools of great importance for the development of fuel cells. Thus, the objective of this work is to carry out the kinetic modeling of glycerol oxidation in a DGFC (direct glycerol fuel cell), considering two different approaches: (1) realistic phenomenological models for the partial oxidation of glycerol in Pt/C, considering its adsorbed intermediates; (2) models of artificial neural networks (ANN—artificial neural networks) for oxidation mainly of PtAg/C and PtAg/MnOx/C. The models were fitted to experimental data already available for validation and determination of their parameters, both using Matlab software, v. R2018a (MathWorks, Natick, MA, USA). Results for the phenomenological models developed showed excellent fits for the polarization curve, with an RMSE (root mean squared error) value on the order of 0.352 to 0.404 mA/cm2, in addition to coverage fractions consistent with the literature for the adsorbed species. The kinetic parameters with the greatest influence on the response of the models were those associated with the consumption of glyceric acid and the formation of tartronic acid and with the dissociative adsorption of water and the formation of Pt-Oads active sites. Regarding the neural models, excellent prediction fits were obtained for all of them, with RMSE values on the order of 0.008 to 0.014 mA/cm2, indicating the possibility of representing the functional interdependence between input variables and the density cell current for cases where it would be too complex to do so via mechanistic modeling (i.e., for PtAg/C and PtAg/MnOx/C oxidation).

The Metal-Oxide Nanoparticle-Aqueous Solution Interface Studied by Liquid-Microjet Photoemission.

ConspectusThe liquid-microjet technique combined with soft X-ray photoelectron spectroscopy (PES) has become an exceptionally powerful experimental tool to investigate the electronic structure of liquid water and nonaqueous solvents and solutes, including nanoparticle (NP) suspensions, since its first implementation at the BESSY II synchrotron radiation facility 20 years ago. This Account focuses on NPs dispersed in water, offering a unique opportunity to access the solid-electrolyte interface for identifying interfacial species by their characteristic photoelectron spectral fingerprints. Generally, the applicability of PES to a solid-water interface is hampered due to the small mean free path of the photoelectrons in solution. Several approaches have been developed for the electrode-water system and will be reviewed briefly. The situation is different for the NP-water system. Our experiments imply that the transition-metal oxide (TMO) NPs used in our studies reside close enough to the solution-vacuum interface that electrons emitted from the NP-solution interface (and from the NP interior) can be detected.We were specifically exploring aqueous-phase TMO NPs that have a high potential for (photo)electrocatalytic applications, e.g., for solar fuel generation. The central question we address here is how H2O molecules interact with the respective TMO NP surface. Liquid-microjet PES experiments, performed from hematite (α-Fe2O3, iron(III) oxide) and anatase (TiO2, titanium(IV) oxide) NPs dispersed in aqueous solutions, exhibit sufficient sensitity to distinguish between free bulk-solution water molecules and those adsorbed at the NP surface. Moreover, hydroxyl species resulting from dissociative water adsorption can be identified in the photoemission spectra. An important aspect is that in the NP(aq) system the TMO surface is in contact with a true extended bulk electrolyte solution rather than with a few monolayers of water, as is the case in experiments using single-crystal samples. This has a decisive effect on the interfacial processes that can occur since NP-water interactions can be uniquely investigated as a function of pH and provides an environment allowing for unhindered proton migration. Our studies confirm that water is dissociatively adsorbed at the hematite surface and molecularly adsorbed at the TiO2 NP surface at low pH. In contrast, at near-basic pH the water interaction is dissociative at the TiO2 NP surface.The liquid-microjet measurements presented here also highlight the multiple aspects of photoemission necessary for a full characterization of TMO nanoparticle surfaces in aqueous environments. For instance, we exploit the ability to increase species-specific electron signals via resonant photoemission, so-called partial electron yield X-ray absorption (PEY-XA) spectra, and from valence photoelectron and resonant Auger-electron spectra. We also address the potential of these resonance processes and the associated ultrafast electronic relaxations for determining charge transfer or electron delocalization times, e.g., from Fe3+ located at the hematite nanoparticle interface into the aqueous-solution environment.

Characterizing Structure-Dependent TiS2/Water Interfaces Using Deep-Neural-Network-Assisted Molecular Dynamics

As a promising layered electrode material, TiS2-based capacitive deionization (CDI) devices for water desalination have attracted significant attention. However, TiS2/H2O interfacial features, potentially important for device optimization, remain unidentified. Using Deep Potential Molecular Dynamics (DPMD), we characterized distinct aqueous interfaces introduced by four TiS2 terminations expected to be present as water intercalates into TiS2, namely, Armchair, Zigzag, Zigzag-L, and Zigzag-R. First, we assessed important representative physical properties of the system to validate the deep potentials (DPs). DPMD simulations agree well with experiments and first-principles simulations, suggesting the DPs are accurate and reliable. Subsequent simulations of these TiS2/water interfaces revealed how TiS2 surface termination influences the structure of interfacial water. This effect is most evident in the first and second water layers close to the TiS2 surface, and more pronounced when spontaneous dissociative adsorption of water occurs. The extent of water dissociation on each surface was evaluated using enhanced sampling. Zigzag-L is the only interface where proton transfer from adsorbed water to TiS2 surface S atoms is thermodynamically and kinetically favored. The coexistence of surface four-fold-coordinated Ti (Ti4c) and one-fold-coordinated S (S1c) is found to be essential to making proton transfer feasible on the Zigzag-L surface. Furthermore, remaining unprotonated S1c atoms can act as good proton acceptors after water dissociation. Thus, TiS2 with Zigzag-L termination may be a surface to avoid in CDI device construction, given that pH fluctuations adversely affect performance. This work provides new understanding of TiS2/H2O interfacial features that could aid future design and optimization of TiS2-based CDI devices for water desalination.

Mechanistic Insights into the High Selectivity and Photocatalytic Activity of Brookite TiO2 toward NOX Abatement

TiO2 nanomaterials are promising photocatalysts for NOx depollution from air under sunlight irradiation. It commonly exists in three phases, i.e., anatase, rutile, and brookite. Anatase, rutile, and a mixture of them are heavily studied. Herein, we have tested the photocatalytic activity of the less studied brookite TiO2 for the NOx depollution from the air. Pure brookite and anatase/brookite mixtures have been synthesized and characterized. Interestingly, we found that brookite TiO2 photocatalyst has a comparable photocatalytic activity to that of the benchmark TiO2 P25, and more importantly, it has higher selectivity toward the conversion of NOx into nitrate ions. The selectivity of brookite TiO2 derived from the TALH precursor is 4.6- and 3.5-fold higher than that of pure anatase and TiO2 P25, respectively. Such impressive selectivity has been explained by measuring the content of physically and chemically adsorbed water, the relative density of defects, and the affinity of NO2 and water adsorption on different anatase and brookite surfaces. The EPR results indicated that brookite TiO2 exhibits a higher density of charge-trapping sites (defects) than anatase. The DFT calculation supported that these defects increase the tendency of brookite (001) surface toward the nondissociative adsorption of NO2, whereas the dissociative adsorption of water is preferred on the perfect surface. It seems that the coexistence of dual sites for the adsorption of molecular NO2 and water-dissociated molecules is crucial for the enhanced selectivity of DeNOx to nitrate ions on brookite TiO2.

Water sorption on pyrochlore – Niobium hydration and calcium susceptibility to leaching unraveled by DFT simulations

Hydration of pyrochlore is a preponderant step during its flotation well before any other surface-reagent interaction to take place. Water adsorption on low-index pyrochlore surfaces is investigated by Density Functional Theory (DFT) simulation, with a focus on the mechanisms of water interaction with surface sites and their coordination. As far as the pyrochlore (100) and (111) surfaces favor the associative physisorption of water, the dissociative chemisorption of water on the (110) surface is by far the most energetically favorable. The affinity of pyrochlore surface to water increases from −81.4 (111), −102.7 (100) to −331.6 kJ/mol (110) leading to decreasing hydrophilic surfaces: (110) ≫ (100) > (111). Water adsorption on the Nb sites located on the (100) surface is unlikely due to the full-coordination state of the exposed Nb. Moreover, the dissociative adsorption of water, driven by a lack of coordination on the (110) surface, would be at the origin of the selective (or non-congruent) dissolution of pyrochlore calcium by weakening its innate bonds. These primary results on the relationship between water and the atomic topology of pyrochlore cleavage planes will help guide the choice of aqueous chemical reagents to be used to address the challenges of this mineral's flotation.

Water adsorption on lead dioxide from abinitio molecular dynamics simulations.

The electrochemically active lead dioxide (β-PbO2) contains the hydrogen (H) species inside the bulk and on the surface. The loss of the surface H species is proposed to be one of the factors in lead-acid battery failure. In this study, water adsorption on β-PbO2 has been investigated using theoretical approaches to reveal the chemical forms of the surface H species and identify a probable cause of H loss mechanisms. For the single water-β-PbO2, density functional theory (DFT) calculations present intact water molecular adsorption on β-PbO2 (100) and dissociative water adsorption on β-PbO2 (110), (101), and (001) surfaces. The geometric distances and the number of hydrogen bonds contribute to the adsorption energy reduction of single water adsorption. For the liquid water-β-PbO2 slab models, DFT-based molecular dynamics simulations observe that the surface lead sites are fully occupied by a hydroxyl group or intact water molecule, and some of the surface oxygens are protonated at 300K. On the β-PbO2 (110) termination, dissociative water adsorption and intact molecular water adsorption occur competitively, leading to about 50% dissociation of adsorbed water molecules. On the β-PbO2 (100), (101), and (001) terminations, the water molecules adsorb preferably in the dissociative form. The surface dependence of water dissociation is explored in terms of hydrogen bonding interactions relevant to adsorbed aqueous species. It is indicated through the Wulff crystal shape that the increase in the β-PbO2 crystallite size may be one of the H loss mechanisms associated with the electrochemically inactive β-PbO2.

Photoinduced Dynamics at the Water/TiO_{2}(101) Interface.

We present a femtosecond time-resolved optical pump-soft x-ray probe photoemission study in which we follow the dynamics of charge transfer at the interface of water and anatase TiO_{2}(101). By combining our observation of transient oxygen O 1s core level peak shifts at submonolayer water coverages with Ehrenfest molecular dynamics simulations we find that ultrafast interfacial hole transfer from TiO_{2} to molecularly adsorbed water is completed within the 285fs time resolution of the experiment. This is facilitated by the formation of a new hydrogen bond between an O_{2c} site at the surface and a physisorbed water molecule. The calculations fully corroborate our experimental observations and further suggest that this process is preceded by the efficient trapping of the hole at the surface of TiO_{2} by hydroxyl species (-OH), that form following the dissociative adsorption of water. At a water coverage exceeding a monolayer, interfacial charge transfer is suppressed. Our findings are directly applicable to a wide range of photocatalytic systems in which water plays a critical role.

Coordination Inversion of the Tetrahedrally Coordinated Ru4f Surface Complex on RuO2(100) and Its Decisive Role in the Anodic Corrosion Process

The c(2 × 2) reconstruction of RuO2(100) leads to unusual and flexible surface functionality in the form of a tetrahedrally coordinated Ru4f surface complex with distinct chemical properties that are important for the anodic activity and stability in water electrolysis. We employ first-principles methods based on density functional theory calculations to elucidate the hybridization of this Ru4f surface species and its rich coordination chemistry. Under oxygen evolution reaction (OER) conditions, the consecutive breaking of structural Ru4f–O back bonds is shown to proceed via the back side attack of Ru4f (akin to the Walden inversion) by dissociative water adsorption and the release of two proton/electron pairs. This inversion step of the coordination environment of a surface transition metal cation is considered to be the key step in the anodic dissolution process. Oxygen evolution over Ru4f on RuO2(100)–c(2 × 2) competes with its dissolution. From ab initio thermodynamics, the inherent OER activity over Ru4f is shown to be lower than that of Ru surface sites on the unreconstructed RuO2(100), while the dissolution propensity of the Ru4f surface complex is higher. This finding calls into question the frequently stated hypothesis that higher activity is correlated with a lower stability of the active center.

Interplay between Facets and Defects during the Dissociative and Molecular Adsorption of Water on Metal Oxide Surfaces

Surface terminations and defects play a central role in determining how water interacts with metal oxides, thereby setting important properties of the interface that govern reactivity such as the type and distribution of hydroxyl groups. However, the interconnections between facets and defects remain poorly understood. This limits the usefulness of conventional notions such as that hydroxylation is controlled by metal cation exposure at the surface. Here, using hematite (α-Fe2O3) as a model system, we show how oxygen vacancies overwhelm surface cation-dependent hydroxylation behavior. Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy was used to monitor the adsorption of molecular water and its dissociation to form hydroxyl groups in situ on (001), (012), or (104) facet-engineered hematite nanoparticles. Supported by density functional theory calculations of the respective surface energies and oxygen vacancy formation energies, the findings show how oxygen vacancies are more prone to form on higher energy facets and induce surface hydroxylation at extremely low relative humidity values of 5 × 10-5%. When these vacancies are eliminated, the extent of surface hydroxylation across the facets is as expected from the areal density of exposed iron cations at the surface. These findings help answer fundamental questions about the nature of reducible metal oxide-water interfaces in natural and technological settings and lay the groundwork for rational design of improved oxide-based catalysts.