Effect of single water adsorption on the bond order of calcium silicates and its implication for hydration variation

The differences in hydration between β-C₂S and M3-C₃S, the main phases of silicate cement, have not been fully investigated. In this study, density functional theory calculations were used to investigate the structure and bond order of β-C₂S and M3-C₃S before and after the molecular and dissociative adsorption of single water atoms. The unit cell of M3-C₃S was found to have some O atoms with lower bond orders than those in β-C₂S, implying higher chemical reactivity of O atoms in M3-C₃S. The total bond orders of water atoms generally decreased after molecular adsorption, but reductions were minimal, and there were even increases, when the hydrogen bonding among H and surface O atoms was very weak in several M3-C₃S surfaces. In the case of dissociative adsorption, the bond orders of water O–H hydroxyl tended to increase, and the other bond orders among water atoms decreased sharply, even to zero in some cases. Moreover, the bond order variations of water atoms of β-C₂S and M3-C₃S in molecular adsorption were highly correlated with the adsorption energy, with correlation coefficients of 0.9070 and 0.8330, respectively. In both molecular and dissociative adsorption of β-C₂S and M3-C₃S, the total bond order among Ca atoms with other surface atoms decreased after the Ca atoms adsorbed water atoms. This phenomenon also appeared in the dissociative adsorption of surface O atoms. In M3-C₃S, the total strength of the surface O atom bonded to other surface atoms after dissociative adsorption was similar to the strength of the surface O–H hydroxyl bond. The special O atoms in M3-C₃S showed a clear layered arrangement on the surfaces. In the case of dissociative adsorption, H atoms were preferentially adsorbed to special O atoms in the surface layer.     

Molecular and dissociative adsorption of a single water molecule on a β‐dicalcium silicate (100) surface explored by a DFT approach

The adsorption of water on a C₂S surface initiates belite to hydrate. In the present work, the adsorption behavior of single water molecule on a β‐C₂S (100) surface is explored using density functional theory (DFT) due to the lack of alternative approaches for direct observation. Four possible calcium atom sites on the β‐C₂S (100) surface slab are considered in our calculations. The results show that water can adsorb on the 2 five‐coordinated calcium sites only via molecular adsorption with adsorption energies of 0.59 and 0.85 eV, respectively, but can dissociate on the other 2 six‐coordinated calcium sites with higher adsorption energies of 0.96 and 0.99 eV, respectively. The energy barriers to the dissociative adsorption of water at the Ca(III) site(0.10 eV) is much lower than that at the Ca(IV) site, indicating that water prefers to adsorb and dissociate on Ca(III) sites. The dissociative adsorption of water causes more obvious surface calcium shifts and Si–O bond length increases than molecular adsorption. The dissociative adsorption of a water molecule changes the electron distribution, and the overlap between Ca 2p and O 2s orbitals leads to new Ca–O bond formations.     

Improved evidence for the existence of an intermediate phase during hydration of tricalcium silicate

Tricalcium silicate (Ca₃SiO₅) with a very small particle size of approximately 50 nm has been prepared and hydrated for a very short time (5 min) by two different modes in a paste experiment, using a water/solid-ratio of 1.20, and by hydration as a suspension employing a water/solid-ratio of 4000. A phase containing uncondensed silicate monomers close to hydrogen atoms (either hydroxyl groups or water molecules) was formed in both experiments. This phase is distinct from anhydrous tricalcium silicate and from the calcium-silicate-hydrate (C-S-H) phase, commonly identified as the hydration product of tricalcium silicate. In the paste experiment, approximately 79% of silicon atoms were present in the hydrated phase containing silicate monomers as determined from ²⁹Si{¹H} CP/MAS NMR. This result is used to show that the hydrated silicate monomers are part of a separate phase and that they cannot be attributed to a hydroxylated surface of tricalcium silicate after contact with water. The phase containing hydrated silicate monomers is metastable with respect to the C-S-H phase since it transforms into the latter in a half saturated calcium hydroxide solution. These data is used to emphasize that the hydration of tricalcium silicate proceeds in two consecutive steps. In the first reaction, an intermediate phase containing hydrated silicate monomers is formed which is subsequently transformed into C-S-H as the final hydration product in the second step. The introduction of an intermediate phase in calculations of the early hydration of tricalcium silicate can explain the presence of the induction period. It is shown that heterogeneous nucleation on appropriate crystal surfaces is able to reduce the length of the induction period and thus to accelerate the reaction of tricalcium silicate with water.     

Hartree–Fock periodic study of the chemisorption of small molecules on TiO2 and MgO surfaces

We present ab initio periodic Hartree–Fock calculations (CRYSTAL program) of the adsorption of small molecules on TiO₂ and MgO. These may be molecular or dissociative, depending on the acidic and basic properties of the molecules in gas phase and of the nature of the surface oxide. For the molecular adsorption, the molecules are adsorbed as bases on Ti(+IV) sites, the adsorption energies correlate with the proton affinities. The dissociations on the surface correlate with the gas phase cleavages of the molecule; they also depend on the surface oxide; the oxygen atom of MgO, in spite of its large charge, is poorly reactive and dissociation on MgO is not favorable.

The surface hydrosyl of MgO are more basic than the O of the lattice and water is not dissociated under adsorption. As experimentally observed, NH₃ adsorbs preferentially on TiO₂ and CO₂ on MgO. However, this difference of reactivity should not be expressed in terms of acid vs basic behavior, but in terms of hard and soft acidity. MgO surface is a “soft” acidic surface that reacts preferentially with the soft base, CO₂.

Another important factor is the adsorbate–adsorbate interaction: favorable cases are the sequence of H-bonds for the hydroxyl groups resulting from the water dissociation and the mode of adsorption for the ammonium ions. Lateral interactions also force the adsorbed CO₂ molecules to bend over the surface, so that their mutual orientation resembles the geometry of the CO₂ dimer.     

聚乙二醇在硅酸二钙表面吸附的分子动力学模拟

采用分子动力学模拟研究了在真空和水溶液环境下聚乙二醇在β-2CaO·SiO₂表面吸附的规律及其机理。在真空环境下聚乙二醇与β-2CaO·SiO₂不同晶面的吸附强弱顺序依次为:(110)>(010)>(011)>(001)≈(101)>(100);而在水溶液环境下其吸附强弱顺序为:(010)≈(110)≈(001)>(011)>(101)>(100)。真空和水溶液环境下在343～363 K时温度对聚乙二醇与β-2CaO·SiO₂(110)晶面相互作用时的单位面积吸附能影响不大,但当在聚合物链节数较小时单位面积吸附能随链节数的增加而明显增加。在水溶液的环境中,分别构造了β-2CaO·SiO₂和聚乙二醇与水分子的径向分布函数,水分子与聚合物、β-2CaO·SiO₂表面之间都存在吸附能,由于水分子较小,其对聚合物与晶面的吸附产生排斥作用,导致聚合物在水环境中与硅酸二钙晶体吸附能降低。     

Nonadiabatic pathways in the dissociative adsorption of simple molecules

Molecular beams and laser spectrometry have been used to study nonadiabatic processes in the interaction of molecules with well-characterized surfaces. The emission of exoelectrons and the formation of O⁻ ions in the interaction of O₂ molecules with a Cs(√3 x √3) structure on Ru(001) is studied as a function of translational energy, extending previously reported results. The interaction of O₂ with an Al(111) surface exhibits an abstraction channel, which is predominant at translational energies smaller than 0.5 eV. In the interaction of NO₂ with an Al(111) surface, the operation of an abstraction channel resulting in O(a) and NO(g) is observed. All three examples are interpreted to indicate the significance of early charge transfer channels in molecular dissociative adsorption processes. Delayed charge transfer may lead to nonadiabatic reaction routes in this scenario.     

Decomposition of N2O over the surface of cobalt spinel: A DFT account of reactivity experiments

The DFT molecular modeling of N₂O decomposition over cobalt spinel (1 0 0) plane was performed using a cluster approach, and applied to rationalize the experimental reactivity data. The energetics of the postulated elementary steps such as N₂O adsorption, N₂O activation through dissociative electron or oxygen atom transfer, surface diffusion of resultant oxygen intermediates, and their recombination into O₂, was evaluated and discussed. The geometry and electronic structure of the implicated active sites and intermediates were determined. Three different transition states were found for the activation of nitrous oxide molecule. In the preferred electron transfer mechanism, involving a monodentate transition state, the N₂O activation and the formation of dioxygen are energetically the most demanding steps, whereas the barrier for the oxygen surface diffusion was found to be distinctly smaller. For the oxygen atom transfer the reaction is energetically constraint by the NO bond-breaking step. The inhibiting effect of co-adsorbed water and oxygen on the particular reaction steps was briefly addressed.     

Methanol Adsorption on V2O3(0001)

Well ordered V₂O₃(0001) layers may be grown on Au(111) surfaces. These films are terminated by a layer of vanadyl groups which may be removed by irradiation with electrons, leading to a surface terminated by vanadium atoms. We present a study of methanol adsorption on vanadyl terminated and vanadium terminated surfaces as well as on weakly reduced surfaces with a limited density of vanadyl oxygen vacancies produced by electron irradiation. Different experimental methods and density functional theory are employed. For vanadyl terminated V₂O₃(0001) only molecular methanol adsorption was found to occur whereas methanol reacts to form formaldehyde, methane, and water on vanadium terminated and on weakly reduced V₂O₃(0001). In both cases a methoxy intermediate was detected on the surface. For weakly reduced surfaces it could be shown that the density of methoxy groups formed after methanol adsorption at low temperature is twice as high as the density of electron induced vanadyl oxygen vacancies on the surface which we attribute to the formation of additional vacancies via the reaction of hydroxy groups to form water which desorbs below room temperature. Density functional theory confirms this picture and identifies a methanol mediated hydrogen transfer path as being responsible for the formation of surface hydroxy groups and water. At higher temperature the methoxy groups react to form methane, formaldehyde, and some more water. The methane formation reaction consumes hydrogen atoms split off from methoxy groups in the course of the formaldehyde production process as well as hydrogen atoms still being on the surface after being produced at low temperature in the course of the methanol ?? methoxy + H reaction.     

The Nature of the Catalytic Sites for H2 Dissociation

Scanning Tunneling Microscopy (STM) can reveal the nature of active sites on the surface of heterogeneous catalysts. This is shown for the case of the dissociation of molecular hydrogen on Pd(111), which has been studied recently both experimentally and theoretically. STM can image in real time to generate movies of adsorbed atoms diffusing on the catalyst surface and forming aggregates. Of particular interest is the behavior near saturation coverage, a situation that is common when catalysts operate under the gas pressures typical of many industrial reactions. Under these conditions, active catalyst sites are formed as a result of density fluctuations that free atoms at the catalyst surface of adsorbates, so that they become available for new reactions. Little is known about the structure of the sites generated in this process. While the end state of a dissociative adsorption of a diatomic molecule requires at least two empty sites to accommodate the reaction products, the initial state where the molecule adsorbs and dissociates, might be more complicated and its nature is unknown. The review shows how STM can provide an improved understanding of the nature of these initial sites.     

Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide

Cerium oxide is a principal component in many heterogeneous catalytic processes. One of its key characteristics is the ability to provide or remove oxygen in chemical reactions. The different crystallographic faces of ceria present significantly different surface structures and compositions that may alter the catalytic reactivity. The structure and composition determine the number of coordination vacancies surrounding surface atoms, the availability of adsorption sites, the spacing between adsorption sites and the ability to remove O from the surface. To investigate the role of surface orientation on reactivity, CeO₂ films were grown with two different orientations. CeO₂(100) films were grown ex situ by pulsed laser deposition on Nb-doped SrTiO₃(100). CeO₂(111) films were grown in situ by thermal deposition of Ce metal onto Ru(0001) in an oxygen atmosphere. The chemical reactivity was characterized by the adsorption and decomposition of various molecules such as alcohols, aldehydes and organic acids. In general the CeO₂(100) surface was found to be more active, i.e. molecules adsorbed more readily and reacted to form new products, especially on a fully oxidized substrate. However the CeO₂(100) surface was less selective with a greater propensity to produce CO, CO₂ and water as products. The differences in chemical reactivity are discussed in light of possible structural terminations of the two surfaces. Recently nanocubes and nano-octahedra have been synthesized that display CeO₂(100) and CeO₂(111) faces, respectively. These nanoparticles enable us to correlate reactions on high surface area model catalysts at atmospheric pressure with model single crystal films in a UHV environment.     

Computer Simulation of Dissociative Adsorption of Water on the Surfaces of Spinel MgAl2O4

Atomistic simulation techniques have been used to model the dissociative adsorption of water onto the low-index {100}, {110}, and {111} surfaces of spinel MgAl₂O₄. The Born model of solids and the shell model for oxygen polarization have been used. The resulting structures and chemical bonding on the clean and hydrated surfaces are described. The calculations show that the dissociative adsorption of water on the low-index surfaces is generally energetically favorable. For the {110} and {111} orientations, the surfaces cleaved between oxygen layers show high absorption and stability. The calculations also show that, for the {111} orientation, the surfaces may absorb chemically water molecules up to ∼90% coverage and have the highest stability. It is suggested that, during fracture, only partial hydration occurs, leading to cleavage preferentially along the {100} orientation.     

Impurity Atoms on Small Transition Metal Clusters. Insights from Density Functional Model Studies

We review our computational studies at the DFT level on small isolated metal clusters of late transition metals that contain atomic (H, C, O) or diatomic (CO, N₂) ligands. These investigations were initiated by the clarification of the structure of iridium and rhodium clusters, as characterized by EXAFS, and then were extended to clusters of other transition metals (Ni, Ru, Pd, Os, Pt). The results suggest that a single H atom hardly changes the structure of a small metal cluster, while the presence of O and C impurity atoms causes large variations in the metal?Cmetal distances. The adsorption of single atoms results in a partial oxidation of the metal moiety, yet addition of an atomic impurity only moderately modifies the electronic properties of small clusters, whereas stronger modifications of the properties are caused when the charge of the metal cluster is varied. The dissociative adsorption of larger amounts of hydrogen, up to 6 H₂ molecules, on metal tetramers causes an elongation of the (average) inter-metallic distances, bringing them close to the experimental values. This body of computational results can be helpful for elucidating the structures of experimentally observed species and for rationalizing their electronic and catalytic properties.     

Surface interaction of quaternary amines with hair

Surface analysis by X-ray photoelectron spectroscopy (XPS) has shown specific 1∶1 (ionic) interaction between cationic alkyl quaternary surfactant molecules and the anionic sulfonate groups present on the hair surface. The primary driving force for the adsorption of alkyl quaternary amine molecules to the surface of the hair from aqueous solution is the ionic interaction between quaternary groups and the surface SO₃ ⁻ on the hair. Cationic quaternary molecules incorporating ester and alcohol functionalities (ester quats) demonstrate a lower number of surface quaternary nitrogens per sulfonate group, indicating an altered surface interaction mechanism. For the ester quats, a combination of electrostatic interaction modes exists in addition to the ionic N⁺/SO₃ ⁻ interaction, specifically, H-bonding interactions of the −C−O, −C−OH, and −C(O)O− polar groups with SO₃ ⁻ and other polar groups on the hair. Surface coverage of the ester quat is not reduced despite the decrease in ionic interaction at the surface. Both types of molecules orient their alkyl tails toward the surface. Molecular dynamics modeling of the surfactant/hair surface interaction indicates higher adsorption energies due to increased dipolar interactions for ester quat molecules.     

The Interaction of Noble Metal With La1–xSrxMnO3 (001) Surface and Catalytic Role for Oxygen Adsorption: A Density Functional Theory Study

Adsorption mechanisms of noble metals (Ag, Pd, Pt) on MnO₂‐terminated (001) surface and their catalytic role for oxygen adsorption have been investigated using the first‐principles density functional theory calculations. The analysis of the adsorption energies reveals that the energetically favorable configuration for Ag and Pd adsorption is at the O site, whereas one for Pt adsorption is at the Mn site. Pt atom exhibits the largest adsorption energy, followed by Pd and Ag atoms. Both bond population and PDOS (partial density of states) analysis confirm the formation of adatom–O–Mn bonds. Adsorption is accompanied by a charge transfer between adatoms and surface atoms. Significantly, we predict that the order on the increase of O₂ adsorption energy follows the Pd > Ag > Pt due to pre‐adsorbed noble metal atoms. The calculated bond length and bond population of O₂ molecule demonstrate that pre‐adsorbed noble metal atoms facilitates O₂ molecule dissociate to O atoms, thus contributing to the surface oxygen diffusion process. Our calculations identify an important catalytic role of noble metal in LSM‐based catalysts, which may improve electrochemical performance for SOFCs cathodes.     

Molecular adsorption on V2O3(0001)/Au(111) surfaces

The adsorption of carbon monoxide (CO), propane (C₃H₈) and propene (C₃H₆) on V₂O₃(0001) films grown on Au(111) was studied by Temperature Programmed Desorption (TPD) and X-ray Photoelectron Spectroscopy (XPS). The “oxidized” surface (i.e., as prepared exhibiting V=O termination), the “reduced” surface (i.e., V=O groups being removed by electron irradiation), as well as the oxygen pre-covered reduced surface were investigated. Both TPD and XPS indicate that the oxidized surface has little affinity for CO adsorption, while the reduced surface readily binds CO (CO amount approx. 10 times higher). Accordingly, CO can be used to titrate the presence or absence of vanadyl oxygen (via adsorption on the vanadium atoms) but also of defects like surface oxygen vacancies. For propane and propene, desorption of the parent molecules was the major process, i.e., surface reactions were absent under the applied conditions. When oxygen was pre-adsorbed on the reduced surface, the adsorption properties resembled that of the oxidized surface, i.e., the vanadyl groups were (partially) re-established. TPD and XPS provide a handle to differentiate the binding sites on the V₂O₃ surface. Dedicated to Prof. Konrad Hayek.     

A comparative theoretical study of Au,Ag and Cu adsorption on TiO<Subscript>2</Subscript> (110) rutile surfaces

The adsorption properties of Au, Ag and Cu on TiO₂ (110) rutile surfaces are examined using density functional theory slab calculations within the generalized gradient approximation. We consider five and four different adsorption sites for the metal adsorption on the stoichiometric and reduced surfaces, respectively. The metal-oxide bonding mechanism and the reactivity of metal atoms are also discussed based on the analyses of local density of states and charge density differences. This study predicts that Au atoms prefer to adsorb at the fourfold hollow site over the fivefold-coordinated Ti(5c) and in-plane and bridging O(2c) atoms with the adsorption energy of ≈0.6 eV. At this site, it appears that the covalent and ionic interactions with the Ti(5c) and the O(2c), respectively, contribute synergistically to the Au adsorption. At a neutral F _s ⁰ center on the reduced surface, Au binds to the surface via a rather strong ionic interaction with surrounding sixfold-coordinated Ti(6c) atoms, and its binding energy is much larger than to the stoichiometric surface. On the other hand, Ag and Cu strongly interact with the surface bridging O(2c) atoms, and the site between two bridging O(2c) atoms is predicted to be energetically the most favorable adsorption site. The adsorption energies of Ag and Cu at the B site are estimated to be ≈1.2 eV and ≈1.8 eV, respectively. Unlike Au, the interaction of Ag and Cu with a vacancy defect is much weaker than with the stoichiometric surface. °This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Surface stabilities of 3C–SiC and H2O adsorption on the (110) surface

First-principles calculations and thermodynamics analyses were combined to study the surface stabilities of 3C–SiC and H₂O adsorption on the (110) surface. The stoichiometric (110) surface was predicted to be generally the most stable. Only at the extremely C-poor condition, the nonstoichiometric Si-terminated (100) could become more energetically favored. The adsorption and dissociation of single H₂O molecule on the 3C–SiC (110) were then comparatively investigated. Calculations show that H₂O molecules prefer to partially dissociate into one hydroxyl OH and one H adsorbed at the top-most Si and C sites, respectively, leading to the formation of a hydrogen network on the surface. The calculated equilibrium adsorption diagram further suggested that the 3C–SiC (110) surface can be only either completely clean or fully covered by the partially dissociated species of H₂O, for a wide range of temperature and the partial potential of H₂O.     

Atomistic understanding of surface wear process of sodium silicate glass in dry versus humid environments

Understanding surface reactions of silicate glass under interfacial shear is critical as it can provide physical insights needed for rational design of more durable glasses. Here, we performed reactive molecular dynamics (MD) simulations with ReaxFF potentials to study the mechanochemical wear of sodium silicate glass rubbed with amorphous silica in the absence and presence of interfacial water molecules. The effect of water molecules on the shear-induced chemical reaction at the sliding interface was investigated. The dependence of wear on the number of interfacial water molecules in ReaxFF-MD simulations was in reasonable agreement with the experimental data. Confirming this, the ReaxFF-MD simulation was used to find further details of atomistic reaction dynamics that cannot be obtained from experimental investigations only. The simulation showed that the severe wear in the dry condition is due to the formation of interfacial Si_substrate–O–Si_{counter_surface} bond that convey the interfacial shear stress to the subsurface and the presence of interfacial water reduces the interfacial bridging bond formation. The leachable sodium ions facilitate surface reactions with water-producing hydroxyl groups and their key role in the hydrolysis reaction is discussed.     

Theoretical study of reduction mechanism of Fe2O3 by H2 during chemical looping combustion

An atomic-level insight into the H2 adsorption and oxidation on the Fe2O3 surface during chemical-looping combustion was provided on the basis of density functional theory calculations in this study.The results indicated that H2 molecule most likely chemisorbs on the Fe2O3 surface in a dissociative mode.The decomposed H atoms then could adsorb on the Fe and O atoms or on the two neighboring O atoms of the surface.In particular,the H2 molecule adsorbed on an O top site could directly form H2O precursor on the O3-terminated surface.Further,the newly formed H-O bond was activated,and the H atom could migrate from one O site to another,consequently forming the H2O precursor.In the H2 oxidation process,the decomposition of H2 molecule was the rate-determining step for the O3-terminated surface with an activation energy of 1.53 eV.However,the formation of H2O was the rate-determining step for the Fe-terminated surface with an activation energy of 1.64 eV.The Fe-terminated surface is less energetically favorable for H2 oxidation than that the O3-terminated surface owing to the steric hindrance of Fe atom.These results provide a fundamental understanding about the reaction mechanism of Fe2O3 with H2,which is helpful for the rational design of Fe-based oxygen car-rier and the usage of green energy resource such as H2.     

Organic molecule intercalation sites in Sr2CaCu2Oy superconductor

The organic molecule adsorption sites in a Sr₂CaCu₂O_y (0^(Sr)212) half unit cell upon water molecule intercalation were estimated by simulation using Molecular Orbital PACkage (MOPAC) program. For water molecules, the unit cell was elongated with increasing the number of molecules. Upon four water molecules intercalated between the two SrO layers, the upper Sr atom moved along the c-axis by 1.49 Å. This value was smaller than but comparable to the experimentally obtained elongation of half of the c-parameter. The primary reason of the elongation is the repulsive force between Sr–H atoms in the two SrO layers. For ethanol and acetone molecules, stable intercalation sites were not found in the 0^(Sr)212 crystal. These results coincided to the experimental results, which did not show intercalations. It was concluded that MOPAC can reproduce the organic molecule intercalation phenomena in oxide crystals.