Silica Surface Chemistry Research Articles

Tetra-Amido Macrocyclic Ligand (TAML) at Silicon(IV): A Structurally Constrained, Water-Soluble Silicon Lewis Superacid.

Tetracoordinate silicon species are typically tetrahedral, weak Lewis acids, and often sensitive to moisture. In this study, we present a tetra-amido macrocyclic ligand (TAML)-substituted Si(IV), isolated as its bis(pyridine) adduct. Due to structural constraint toward anti van't-Hof/Le Bel geometry, this compound exhibits Lewis superacidity and effectively catalyzes the hydroboration of pyridine. Kinetic and computational analyses of the catalytic cycle reveal that TAML-Si(IV) acts as a hydride transfer agent, and the hydrido silicate key intermediate is isolated. Notably, the Lewis acid is highly soluble (5 g/L) and long-term stable in water. Unlike previously described silicon-H2O adducts, the bound water becomes substantially acidified, reaching the Bro̷nsted superacidity range. A comparison of water affinity versus pKa lowering confirms our previous theory of the strength and the effect of Lewis acids. Overall, the compound's unlimited water compatibility and its mechanistically understood catalytic efficiency mark significant progress in applying structural constraint strategies for p-block element-based catalysis, while the acidification touches critical aspects of zeolite and silica surface chemistry.

Effect of Preparation Methods on the Interface of LiBH4/SiO2 Nanocomposite Solid Electrolytes.

Nanocomposites of complex metal hydrides and oxides are promising solid state electrolytes. The interaction of the metal hydride with the oxide results in a highly conducting interface layer. Up until now it has been assumed that the interface chemistry is independent of the nanoconfinement method. Using 29Si solid state NMR and LiBH4/SiO2 as a model system, we show that the silica surface chemistry differs for nanocomposites prepared via melt infiltration or ball milling. After melt infiltration, a Si···H···BH3 complex is present on the interface, together with silanol and siloxane groups. However, after ball milling, the silica surface consists of Si- H sites, and silanol and siloxane groups. We propose that this change is related to a redistribution of silanol groups on the silica surface during ball milling, where free silanol groups are converted to mutually hydrogen-bonded silanol groups. The results presented here help to explain the difference in ionic conductivity between nanocomposites prepared via ball milling and melt infiltration.

Mitigation of Silicon Contamination in Fuel Cell Gasket Materials through Silica Surface Treatment.

Gaskets and seals are essential components in the operation of proton exchange membrane (PEM) fuel cells and are required for keeping hydrogen and air/oxygen within their individual compartments. The durability of these gaskets and seals is necessary, as it influences not only the lifespan but also the electrochemical efficiency of the PEM fuel cell. In this study, the cause of silicon leaching from silicone gaskets under simulated fuel cell conditions was investigated. Additionally, to reduce silicon leaching, the silica surface was treated with methyltrimethoxysilane, vinyltriethoxysilane, and (3,3,3-trifluoropropyl)trimethoxysilane. Changes in the silica surface chemistry were investigated by scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis, elemental analysis, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. Inductively coupled plasma-optical emission spectroscopy analysis revealed that surface-treated silica was highly effective in reducing silicon leaching.

Photothermally heated colloidal synthesis of nanoparticles driven by silica-encapsulated plasmonic heat sources

Using photons to drive chemical reactions has become an increasingly important field of chemistry. Plasmonic materials can provide a means to introduce the energy necessary for nucleation and growth of nanoparticles by efficiently converting visible and infrared light to heat. Moreover, the formation of crystalline nanoparticles has yet to be included in the extensive list of plasmonic photothermal processes. Herein, we establish a light-assisted colloidal synthesis of iron oxide, silver, and palladium nanoparticles by utilizing silica-encapsulated gold bipyramids as plasmonic heat sources. Our work shows that the silica surface chemistry and localized thermal hotspot generated by the plasmonic nanoparticles play crucial roles in the formation mechanism, enabling nucleation and growth at temperatures considerably lower than conventional heating. Additionally, the photothermal method is extended to anisotropic geometries and can be applied to obtain intricate assemblies inaccessible otherwise. This study enables photothermally heated nanoparticle synthesis in solution through the plasmonic effect and demonstrates the potential of this methodology.

SiO2/Zn0.4Co0.6Fe2O4 aerogel: an efficient and reusable superparamagnetic adsorbent for oily water remediation.

Magnetic SiO2/Zn0.4Co0.6Fe2O4 aerogels were successfully prepared by sol-gel method with two different drying steps: ambient pressure drying (APD) and freeze-drying (FD). The surface chemistry of silica was modified to be hydrophobic by oleic acid. The prepared materials were fully characterized, displaying superparamagnetic behavior with saturation magnetizations of 10.2 and 15.1 emu g-1, and contact angles of ∼130° and ∼140° for the materials prepared by the APD and FD methods, respectively, indicating the hydrophobic surfaces of the prepared materials. This hydrophobicity allows the efficient separation of oil. Specifically, as high as 1.7 and 2 g g-1 adsorption capacities were obtained when using APD-dried and FD-dried silica aerogels, respectively, suggesting the preference for the FD method. Additionally, magnetic recovery and reuse of the adsorbents were successfully implemented in an attempt to reduce the overall practical application costs. To sum up, the prepared materials are good candidates for oil removal from wastewater and the protection of the environment.

Using low-field NMR relaxation to optimise particulate dispersions

Formulation of particulate dispersions is a difficult industrial problem, with a multitude of system details influencing the final outcome. Solvent relaxation NMR is shown to help optimise the formulation of particulate dispersions of a range of widely used commercial silicas. Solvent at the particle interface is sensitive to details of the formulation, and it is shown that the average solvent spin-relaxation time in a dispersion can be used to monitor wetted surface area, sample sedimentation, and additive amounts; chemical syntheses and mechanical degradation of silicas are also monitored to optimise the dispersions. The experiments, which can be carried out on bench-top or on-line spectrometers, are not limited to silicas and can be generalised to other particles in a range of aqueous and non-aqueous dispersions, providing useful feedback to the formulator anywhere surfactants, polymers, pH, ionic strength, Hamaker constants, and surface charge play a role in stabilisation. • Rapid NMR relaxation measurements reveal variation in silica surface chemistry. • Breakup of silica aggregates is monitored by NMR relaxation to optimise processing. • NMR relaxation measurements provide facile quality control tests for hydrogels. • Silica particle syntheses are monitored by NMR relaxation.

A Comparative Study of PMETAC-Modified Mesoporous Silica and Titania Thin Films for Molecular Transport Manipulation.

The manipulation and understanding of molecular transport across functionalized nanopores will take us closer to mimicking biological membranes and thus to design high-performance permselective separation systems. In this work, Surface-initiated atom transfer radical polymerization (SI-ATRP) of (2-methacryloyloxy)-ethyltrimethylammonium chloride (METAC) was performed on both mesoporous silica and mesoporous titania thin films. Pores were proven to be filled using ellipsometry and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Furthermore, the employed method leads to a polymer overlayer, whose thickness could be discriminated using a double-layer ellipsometry model. Cyclic voltammetry experiments reveal that the transport of electrochemically active probes is affected by the PMETAC presence, both due to the polymer overlayer and the confined charge of the pore-tethered PMETAC. A more detailed study demonstrates that ion permeability depends on the combined role of the inorganic scaffolds' (titania and silica) surface chemistry and the steric and charge exclusion properties of the polyelectrolyte. Interestingly, highly charged negative walls with positively charged polymers may resemble zwitterionic polymer behavior in confined environments.

Reversible Adsorption of Polycarboxylates on Silica Fume in High pH, High Ionic Strength Environments for Control of Concrete Fluidity.

Polycarboxylate-based superplasticizers are essential for production of ultrahigh-performance concrete (UHPC), facilitating particle dispersion through electrostatic repulsion and steric hindrance. This study examines for the first time the effect of changes in pH, ionic strength, and charge on the adsorption/desorption behavior of a polycarboxylate-based superplasticizer on silica fume in aqueous chemistries common in low-CO2 UHPC. Data from total organic carbon measurements, Fourier transform infrared and nuclear magnetic resonance spectroscopy, and zeta potential measurements reveal the silica surface chemistry and electrokinetic properties in simulated UHPC. Addition of divalent cations (Ca2+) results in polycarboxylate adsorption on silica fume via (i) adsorption of Ca2+ ions on the silica surface and a negative zeta potential of lower magnitude on the silica surface and (ii) reduction of polycarboxylate anionic charge density due to complexation with Ca2+ ions and counter-ion condensation. Addition of OH– ions results in polycarboxylate desorption via deprotonation of silanol groups and a negative zeta potential of greater magnitude on the silica surface. Simultaneous addition of both Ca2+ and OH– results in rapid polycarboxylate desorption via (i) formation of an electric double layer and negative zeta potential on the silica surface and (ii) an increase in polycarboxylate anionic charge density due to deprotonation of the carboxylate groups in the polymer backbone, complexation with Ca2+ ions, and counter-ion condensation. This provides an explanation for the remarkable fluidizing effect observed upon addition of small amounts (1.0 wt %) of a solid, powdered Ca source to fresh, low-CO2, UHPC, which exhibits significantly higher fresh state pH (>13) than those based on Portland cement (pH 11).

Nanopore networks in colloidal silica assemblies characterized by XCT for confined fluid flow modeling

Fluid flow through nanopore structures has exhibited different behavior than that described by Darcy's law, derived from pore networks of micrometer scale. Pressure assemblies of colloidal silica spheres of specified diameters from 94 to 620 nanometers were prepared as model nano-porous media. The smaller silica spheres tended to form random packing, but some substantial ordering was found in the packing of the larger silica spheres. X-ray computed tomography (XCT), with a voxel resolution of 16 nm, was used to characterize the nanopore networks. The porosity of the Nano-XCT pore network (34%) was less than the total porosity of the assemblies as determined by X-ray attenuation (52%), possibly due to the limits of voxel resolution during segmentation. Fluid flow in the nanopore networks was simulated using the single-phase Lattice Boltzmann Method, and the simulated permeability was compared with the empirical and experimental values. Based on our characterization, although a well-ordered packing of silica spheres was not achieved, it was found that the nanopore networks in the colloidal silica assemblies had pore size distributions corresponding to the particle sizes. The simulated permeability was less than the experimental measurement for water flow, but the complex packing of silica spheres and surface chemistry issues need to be considered in future research. 3D X-ray CT raw images, nanopore networks, and LBM simulated flow channels in assemblies of 140 nm (left) and 620 nm (right) colloidal silica spheres (voxel resolution 16 nm). • Pressure assemblies of silica spheres with SdFFF validated particle sizes were made. • Total porosity of the assemblies was measured by an X-ray attenuation approach. • Pore networks were analyzed by Nano-XCT at a voxel resolution of 16 nm. • Fluid flow in nanopore networks was simulated by single-phase LBM.

The impact of the silica gel structure and surface chemistry on the melting of aliphatic nanocrystals: Thermodynamic model and experiment

Phase transitions in nano-sized systems are of fundamental importance in a variety of fields, including sustainable energy and the pharmaceutical industries. Here we report the thermal properties of undecylenic acid nanocrystals in silica gel pores of different sizes and the chemical composition of the pores’ surface. The results of N2 absorption at 77 K, thermogravimetric method, powder XRD method, and differential scanning calorimetry were analyzed to gain an insight into the processes accompanying the phase transition. We using a thermodynamic model of nanocrystal melting in an open porous system and analyze temperature dependence of the effective size of pores, as well as the dependence of the specific heat of melting on the effective size of the pores. This model helps us obtain the following properties of the undecylenic acid: the density of nanocrystals, pressure inside the nanocrystal, the relation between the surface tension coefficients and specific entropies on the nanocrystal-porous matrix interface and melt-porous matrix interface. We demonstrate that as the nanocrystals of the undecylenic acid form in the cavities of the porous matrix, the pressure in such nanocrystals, and thus their densities are much lower than pressure and density in bulk crystals of the undecylenic acid. However, when the crystallization of the nanocrystals occurs in the presence of aliphatic chains grafted on the silica gel pore walls, these chains become embedded into nanocrystals. As the result, the character of the change of properties reverses: both the pressure in the undecylenic acid nanocrystals and their density become larger than those for a bulk undecylenic acid crystal. Throughout the paper, we also contrast the behaviour of a polar undecylenic acid in pores with that of nonpolar 1-octadecen molecules.

Functionalized Nanosilica for Vulcanization Efficiency and Mechanical Properties of Natural Rubber Composites

Accelerator functional character was introduced on nanosilica by chemical reaction of sodium isopropyl xanthate (SIPX) with nanosilica (NS). Functional characteristics of nanosilica were confirmed by elemental analysis, thermogravimetric analysis, and infrared spectroscopy. This SIPX functionalized nanosilica (SIPX-NS) incorporated natural rubber (NR) composites were used to evaluate the dispersion of silica in rubber and also the interaction between rubber and filler. The finely dispersed SIPX-NS particles in the NR matrix are revealed from the morphological analysis. Subtle changes in the surface chemistry of silica had a profound influence on dispersibility in the NR matrix. NR 4SIPX-NS composite showed an increase in tensile strength by 10%, flex crack initiation resistance by 13%, tensile strength retention by 16% and cure time reduced by 2 min relative to those of NR 3NS composite. This simple, efficient and cost-effective surface modification of silica improved the vulcanization efficiency and mechanical performance of NR composites and has great potential in the fabrication of high-performance polymer composites.Graphical abstract

Polythiolactone-Decorated Silica Particles: A Versatile Approach for Surface Functionalization, Catalysis and Encapsulation.

The surface chemistry of colloidal silica has tremendous effects on its properties and applications. Commonly the design of silica particles is based on their de novo synthesis followed by surface functionalization leading to tailormade properties for a specific purpose. Here, the design of robust “precursor” polymer‐decorated silica nano‐ and microparticles is demonstrated, which allows for easy post‐modification by polymer embedded thiolactone chemistry. To obtain this organic‐inorganic hybrid material, silica particles (SiO2P) were functionalized via surface‐initiated atom transfer radical polymerization (SI‐ATRP) with poly(2‐hydroxyethyl acrylate) (PHEA)‐poly(thiolactone acrylamide (PThlAm) co‐polymer brushes. Exploiting the versatility of thiolactone post‐modification, a system was developed that could be used in three exemplary applications: 1) the straightforward molecular post‐functionalization to tune the surface polarity, and therefore the dispersibility in various solvents; 2) the immobilization of metal nanoparticles into the polymer brushes via the in situ formation of free thiols that preserved catalytic activity in a model reaction; 3) the formation of redox‐responsive, permeable polymer capsules by crosslinking the thiolactone moieties with cystamine dihydrochloride (CDH) followed by dissolution of the silica core.

Molecular dynamics simulation of thermal degradation of silicone grease using reactive force field

AbstractSilicone grease, consisting of polydimethylsiloxane (PDMS) chains and silica, has been widely used in electrical power systems; this causes thermal aging of silicone grease at high temperatures. In this study, the thermal degradation process of silicone grease was analyzed at different temperatures using reactive force field (ReaxFF). The effects of different factors, such as silica surface chemistry and oxygen content, on the final products have been studied. The results showed that the final products can be divided into two main categories: small gaseous molecules and large‐molecule products. The number of gaseous hydrocarbon products and their unsaturation increased with increasing temperature. The large‐molecule products were consisted of silica and surrounding PDMS chains, which were broken and reorganized during the thermal degradation process. The time interval required for the formation of the large‐molecule products is larger when silica with a modified surface is used. The addition of oxygen during thermal degradation provided a new decomposition route. The O/Si ratio in the residue of silica grease increased while the C/Si ratio decreased with the increasing oxygen content. A new method for the generation of SiO2 residues in a sufficient oxygen environment was proposed based on the reactions between oxygen and Si–CH3.

Influence of Drug-Silica Electrostatic Interactions on Drug Release from Mesoporous Silica-Based Oral Delivery Systems.

Mesoporous silica particles are attractive carriers for poorly soluble drugs whereby confinement of drugs in the mesopores leads to amorphization, which makes them potential carriers for enhanced oral delivery. However, interactions between the drug molecules and the silica surface can lead to incomplete drug release. The strength of the interaction depends on the silica surface chemistry, which varies as a function of pH, as well as on drug chemistry and ionization states. Herein, the adsorption and dissolution behavior of weakly basic drugs were evaluated as a function of pH to understand the impact of electrostatic interactions on the performance of mesoporous silica-based formulations. A higher adsorption was noted when the drug interacted with the silica surface via electrostatic interactions compared to hydrogen bonding. Higher adsorption, in turn, led to a lower extent of drug release. In two-stage release studies of drugs with pKa values close to the intestinal pH, a shift from low to higher pH solutions resulted in a decrease in the solution concentration. Further investigations demonstrated that this was due to readsorption of the drug, initially released in the acidic medium when the pH was increased. Two-stage release studies were also coupled with mass transport measurements. Only a slight improvement in drug release due to simultaneous absorption across a membrane was observed, suggesting strong drug adsorption to the silica surface arising from favorable electrostatic interactions, which diminishes the effect of sink conditions provided by the absorptive environment. This study highlights that physiological parameters, such as solution pH, are important considerations when designing mesoporous silica-based formulations for poorly soluble drugs. It also underscores the importance of incorporating in vivo-relevant conditions in in vitro testing to better evaluate these complex formulations due to the notable effect of dissolution media on the release behavior.

Interactions at the Silica-Peptide Interface: Influence of the Extent of Functionalization on the Conformational Ensemble.

In this contribution, the effect of silica particle size (28 and 210 nm) and surface chemistry (i.e., hydroxyl, methyl, or amino groups) on peptide binding response is studied with a specific emphasis on the effect of the extent of functionalization on binding. Exhaustive characterization of the silica surfaces was crucial for knowledge of the chemistry and topography of the solid surface under study and, thus, to understand their impact on adsorption and the conformational ensemble of the peptides. The extent of surface functionalization was shown to be particle-size dependent, a higher level of 3-aminopropyl functionality being obtained for smaller particles, whereas a higher degree of methyl group functionality was found for the larger particles. We demonstrated that peptide interactions at the aqueous interface were not only influenced by the surface chemistry but also by the extent of functionalization where a "switch" of peptide adsorption behavior was observed, whereas the changes in the conformational ensemble revealed by circular dichroism were independent of the extent of functionalization. In addition to electrostatic interactions and hydrogen bonding driving interaction at the silica-peptide interface, the data obtained suggested that stronger interactions such as hydrophobic and/or covalent interactions may moderate the interaction. The insights gained from this peptide-mineral study give a more comprehensive view of mechanisms concerning mineral-peptide interactions which may allow for the design and synthesis of novel (nano)materials with properties tailored for specific applications.

Effect of surface chemistry and morphology of silica on the thermal and mechanical properties of silicone elastomers

ABSTRACTIn this study, high‐temperature vulcanized silicone rubbers (HTV‐SRs) using fumed silica (FSi), precipitated silica (PSi), and modified precipitated silica (MPSi) as reinforcing fillers were prepared. The effect of morphology and surface chemistry of the silica on the thermal and mechanical properties of the resultant silicone rubbers was investigated using curing rheometer, scanning electron microscopy, mechanical test, and dynamic mechanical analysis. The thermo‐oxidative stability and solvent resistance of the vulcanized silicone rubbers were further evaluated via heat ageing test, extraction, and swelling experiments. It is shown that the mechanical properties (tensile modulus and tensile strength) of the as‐prepared HTV‐SRs are in the order of FSi > PSi > MPSi, which could be attributed to the molecular interaction between the filler and the matrix. FSi has the highest surface area, which enhances the hydrogen bonding interaction between the filler and the silicone matrix; while MPSi, in which part of SiOH groups have been consumed during modification, shows the weakest interaction among the three. The filler–matrix interaction could also explain the lowest swelling and sol fraction in FSi‐filled HTV‐SR, and the low viscosity and good processibility of PSi‐ and MPSi‐filled HTV‐SR. Furthermore, it is also shown that the MPSi‐filled HTV‐SR exhibits the highest retention of mechanical properties after thermal aging at 250 °C for 24 h, which could be attributed to the lowest acidity of the fillers. The possible mechanism for acid catalyzed hydrolytic chain scission and intramolecular chain backbiting has been proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46646.

Preparation of silica coated and 90Y-radiolabeled β-NaYF4 upconverting nanophosphors for multimodal tracing

Rare-earth (RE) compounds have been actively pursued for therapeutic and diagnostic applications due to their ability to upconvert near infrared light into the UV–vis range. Through nanoengineering and bottom-up synthesis, additional functionality can be added to these upconverting systems. Herein, we report the synthesis of 90Y-doped β-NaYF4:Er, Yb upconverting nanophosphors (UCNPs) to enable β-particle emission and upconversion by the same UCNP. To homogenously incorporate the radionuclides, we employ a hydroxide metathesis method to produce the RE precursor required for the solvothermal synthesis of monodisperse UCNPs. Once incorporated, we find that the β-emitting 90Y dopants do not influence the energy pathways required for upconversion, enabling simultaneous radio- and optical-tracing. The resulting large (>100 nm in height and width), anisotropic, 90Y-radiolabeled β-NaYF4 UCNPs are then coated with silica using a modified, micelle-driven Stöber process to enable their dispersion in polar solvents. Doing so highlights the importance of surfactant (Igepal CO-520) and silica source (tetraethyl orthosilicate) interactions to the continuity of the silica shell and makes the vast library of silica surface chemistry and functionality accessible to upconverting radiotracers.

Significantly improved rubber-silica interface via subtly controlling surface chemistry of silica

It has been commonly acknowledged that particle dispersion and interfacial interactions are vital in determining the ultimate performance of polymer composites. However, the interplay between dispersibility and interfacial interaction in polymer composites has not been explicitly unraveled. In this contribution, a series of silica with controlled surface chemistry are prepared to reveal the effects of subtle change in surface property of filler on the structures and mechanical performance of the rubber composites. On the basis of thermodynamic theory, the dispersibility of modified silica in rubber is quantitatively evaluated by using surface energy. The modified silica was introduced into styrene-butadiene rubber (SBR) to investigate the effects of surface modification on the dispersion of silica and interfacial interaction of the rubber composites. It has been demonstrated that subtle change in surface chemistry of silica drastically improves its dispersibility in rubber matrix, leading to much improved accessible surfaces and hence much complete interfacial reaction. At very low grafting content (0.2 molecule/nm2), improved modulus (44%) and wet-traction (54%), together with reduced rolling-resistance (11%), are concurrently observed.

Coordination and silica surface chemistry of lanthanides (III), scandium (III) and yttrium (III) sorption on 1-(2-pyridylazo)-2-napththol (PAN) and acetylacetone (acac) immobilized gels

This article focuses on identifying the coordination and silica surface chemistry of PAN immobilized mesoporous silica gel in the adsorption of Rare earth elements (REE) in comparison to acetylacetone (acac) immobilized gel. PAN is used as an analytical reagent since it has both acidic (pKa 1.9) and basic (pKa 12.2) properties. A strategy for the adsorption of REE has been developed through the analysis on the adsorption of light rare earths (LREEs) and heavy rare earths (HREEs). In this study, the separation of REEs is achieved via the –N group of pyridine/ azo and –OH group of PAN modified silica, at different conditions. The REEs were studied based on different parameters such as pH, kinetics, metal loadings, binding sites, temperature etc. and distinct differences have been observed in separation between ‘d’ and ‘f’ block elements. Ionic radii, lanthanide contraction and REE tetrad effect impact the adsorption process for different pH and metal loading conditions. This eventually influences the binding mechanism as well. The affinity of the modified gel was towards LREEs at lower pHs and HREEs in higher regime. As a validation attempt, the developed separation strategy has been employed in investigating under natural water conditions for varying REE concentration and pH in the presence of competing ions. Silica gel with PAN (SEP) modifications performed superior to Acac modifications (SEA) in terms of REE adsorption under all conditions. The behavior was coherent for both single and multi-component systems where HREE adsorption showed temperature dependency. As SEP demonstrated adsorption even in the acidic range (pH 2), it has the potential to serve a wide range of applications involving acidic industrial waste such as mine water.

The elusive silica/water interface: isolated silanols under water as revealed by vibrational sum frequency spectroscopy.

It has been long recognized that the surface chemistry of silica, and in particular the type and relative amount of surface bound silanol groups, plays a critical role in many of the properties associated with the material, where a typical example is the discrepant adsorption behavior observed depending on the pretreatment history of the surface. However, in spite of its importance, the direct probing of specific surface silanol groups under water has been hampered by instrumental limitations. Here we make use of vibrational sum frequency spectroscopy (VSFS) to first, identify under water the OH stretch of isolated surface silanols, and second, explore its acid/base behavior and dependence on the surface pretreatment method. The properties of other types of silanol groups (i.e. hydrogen bonded/geminal) are also inferred from the data. The ability to directly probe these functional groups under water represents a crucial step to further improving our understanding of this widely used mineral oxide.