Correlation between surface charge and hydration on mineral surfaces in aqueous solutions: A critical review

Surface charges and hydration are predominant properties of colloidal particles that govern colloidal stability in aqueous suspensions.These properties usually coexist and interact with each other.The correlation between the surface charge and hydration of minerals is summarized on the basis of innovative experimental,theoretical,and molecular dynamics simulation studies.The factors affecting the adsorption behavior of ions and water molecules,such as ion concentration,ion hydration radius and valence,and surface properties,are discussed.For example,the hydration and adsorption states completely differ between monovalent and divalent ions.For ions of the same valence,the effect of surface charge on the hydration force follows the Hofmeister adsorption series.Electrolyte concentration exerts a significant effect on the hydration force at high ion concentrations.Meanwhile,the ion correlations in high-concentration electrolyte systems become long range.The interfacial water structure largely depends on surface chemistry.The hydration layer between different surfaces shows large qualitative differences.

Dynamic Simulation on Surface Hydration and Dehydration of Monoclinic Zirconia

The commonly used oxide-supported metal catalysts are usually prepared in aqueous phase,which then often need to undergo calcination before usage.Therefore,the surface hydration and dehydration of oxide supports are critical for the realistic modeling of supported metal catalysts.In this work,by ab initio molecular dynamics(AIMD)simulations,the initial anhydrous monoclinic ZrO_(2)(111)surfaces are evaluated within explicit solvents in aqueous phase at mild temperatures.During the simulations,all the two-fold-coordinated O sites will soon be protonated to form the acidic hydroxyls(HO_(L)),remaining the basic hydroxyls(HO^(∗))on Zr.The basic hydroxyls(HO^(∗))can easily diffuse on surfaces via the active proton exchange with the undissociated adsorption water(H_(2)O^(∗)).Within the temperatures ranging from 273 K to 373 K,in aqueous phase a certain representative equilibrium hydrated m-ZrO_(2)(¯111)surface is obtained with the coverage(θ)of 0.75 on surface Zr atoms.Later,free energies on the stepwise surface water desorption are calculated by density functional theory to mimic the surface dehydration under the mild calcination temperatures lower than 800 K.By obtaining the phase diagrams of surface dehydration,the representative partially hydrated m-ZrO_(2)(111)surfaces(0.25≤θ<0.75)at various calcination temperatures are illustrated.These hydrated m-ZrO_(2)(111)surfaces can be crucial and readily applied for more realistic modeling of ZrO_(2) catalysts and ZrO_(2)-supported metal catalysts.

Is Water Physisorption Reversible for TiO_2 Nanocrystals? A Combinational Spectral Study

In this work,the nature of physisorbed water and its impacts on the structure,surface chemistry,and proton conduction properties of TiO2 nanocrystals were investigated by a combinational spectral technique.All TiO2 nanocrystals were directly prepared by a hydrothermal method,which showed highly hydrated and sulfated surfaces.The surface water molecules were indicated to exist in a wide set of energetically nonequivalent surface hydration groups,leading to the removal of physisorbed and chemisorbed water in sequence with increasing temperature.After heating treatment at 100 ℃ in air,physisorbed water layers were recovered with no significant impacts on the TiO2 nanostructure.On the other hand,when treated at the same temperature in vacuum,the recovery of physisorbed water layers was partially reversible,while a new hydration state appeared due to the filling of the high-energy adsorption sites by water molecules,which led to a significant increase in the amount of water molecules for surface hydration and an accelerated dehydration process toward lower temperature.As a result,an abnormal increase was observed in proton conductivity.These observations were explained in terms of thermally induced changes of surface chemistry and the amount of hydrated water.The results reported in this work are important,which may help understand the roles that the physisorbed water plays in stabilizing the nanostructures and therefore could have a broad class of implications.

The effect of SiO2 nanoparticles derived from hydrothermal solutions on the performance of portland cement based materials

The nanoparticles of SiO2 were used in cement systems to modify the rheological behavior, to enhance the reactivity of supplementary cementitious materials, and also to improve the strength and durability. In this research, low-cost nano-SiO2 particles from natural hydrothermal solutions obtained by membrane ultrafiltration and, optionally, by cryochemical vacuum sublimation drying, were evaluated in portland cement based systems. The SiO2-rich solutions were obtained from the wells of Mutnovsky geothermal power station （Far East of Russia）. The constant nano-SiO2 dosage of 0.25% （as a solid material by weight of cementitious materials） was used to compare the cement systems with different nanoparticles against a reference mortar and a commercially available nano-SiO2. Nanoparticles were characterized by X-Ray Diffraction （XRD）, BET Surface Area, Scanning Electron Microscope （SEM） and Fourier Transform Infrared （FTIR） spectroscopy techniques. It was demonstrated that the addition of polycarboxylate ether superplasticizer and the dispersion treatment using an ultrasound processor can be used to facilitate the distribution ofnano-SiOz particles in the mixing water. The effect ofnano-SiO2 particles in portland cement mortars was investigated by evaluating the flow, heat of hydration and compressive strength development. It was demonstrated that the use ofnano- SiO2 particles can reduce the segregation and improve strength properties.