A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species

Dissolution, selective leaching, and stress-corrosion cracking are all processes which can degrade the performance of silica and silicate glasses exposed to aqueous environments. Reactions which corrode glass in water include hydration, hydrolysis and condensation, and ion-exchange processes. Techniques such as solid-state nuclear magnetic resonance, Raman and Fourier transform infrared spectroscopies, pH stat titrations and elemental depth profiling have been used to establish the relative importance of the above reactions on glass degradation as a function of solution pH and composition, temperature and stress level. This paper reviews results obtained for silica, alkali silicate, and alkali boro- and aluminosilicate glasses. For most glasses, the rate at which water enters the glass structure controls the kinetics of the other glass-water reactions, explaining the corrosion characteristics of different glass compositions.

Molecular mechanisms for corrosion of silica and silicate glasses

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments / Albert Rimola;Dominique Costa;Mariona Sodupe;Jean-François Lambert;Piero Ugliengo. In: CHEMICAL REVIEWS. ISSN 0009-2665. STAMPA. 113:6(2013), pp. 4216-4313. Original Citation: Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

/pdf/silica-surface-features-and-their-role-in-the-adsorption-of-2hhuc04ksj.pdf

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

Nanosized ZSM5 zeolites with microcrystal dimensions in the 20–120 nm range have been characterized by means of IR spectroscopy and HRTEM microscopy. The vibrational spectrum of the OH groups on the external and internal surfaces of H-ZSM5 and Na-ZSM5 samples of different crystallite dimensions has been investigated. For the sake of comparison the spectra of silicalite samples containing different concentrations of sodium and aluminium are also shown. For this purpose high-purity silicalite samples were prepared following a novel synthesis route.Carbon monoxide (a very weak Lewis base) was used to probe the acidity present on the external and internal surfaces of the zeolites through formation of 1 : 1 adducts with silanols (both internal and external), Bronsted-acid groups (both framework and extraframework), Na+ ions, and Lewis Al3+ centres (in extraframework and framework positions). The IR-active CO stretching modes of the complexes are shifted to higher wavenumber with respect to the free molecule; the positive shift can be used to estimate the acid strength. CO that was physically adsorbed in the zeolite channels has also been investigated.

Low-temperature Fourier-transform infrared investigation of the interaction of CO with nanosized ZSM5 and silicalite

The surface composition of a quartz surface reacted with various aqueous solutions of pH 0−10 was qualitatively and quantitatively evaluated using X-ray photoelectron spectroscopy (XPS). The positions and intensities of the recorded Si 2p and O 1s lines change depending on solution conditions. The O 1s line, where the position varies more significantly, was analyzed in detail showing three components corresponding to three surface species:  >SiOH2+, >SiOH0, and >SiO- (where > represents the bulk quartz). The changes in the Si 2p spectra support these findings. The atomic ratio between the surface oxygen and silicon atoms was found to be 1.8. These data allow proposing a two-step deprotonation model of the quartz surface where two surface oxygen atoms are bonded to one silicon surface atom and where the most deprotonated surface sites show the SiO- configuration. Physisorbed water in the amount of around 10% of the monolayer was also found on all samples under spectroscopic investigation. The density of th...

Evidence of the Existence of Three Types of Species at the Quartz−Aqueous Solution Interface at pH 0−10: XPS Surface Group Quantification and Surface Complexation Modeling

Infrared studies of reactions on oxide surfaces. 5. Lewis acid sites on dehydroxylated silica

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Infrared studies of reactions on oxide surfaces. 5. Lewis acid sites on dehydroxylated silica