In this work, we have systematically investigated the effect of the Al content on the number and location of bridging hydroxyls (Brønsted acid sites) and terminal hydroxyls (terminal silanol sites) in ZSM-5 zeolites with varying silica-alumina ratio (SAR ¼ SiO 2 /Al 2 O 3 ) using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) without molar extinction coefficients. Two base probe molecules with different kinetic diameters, pyridine (5.7Å) and collidine (7.4Å), were used. The total content of Brønsted acid sites is obtained by elemental analysis of the proton form and sodium exchanged form of ZSM-5. To quantify the number of internal and external Brønsted acid sites the change in area of the Brønsted acid site peak in the O-H stretching region is then used; thus, the need for molar extinction coefficients to quantify Brønsted acid sites is thereby eliminated. The results reported here show that for ZSM-5 the number of external Brønsted sites, in absolute terms, increases with increasing total Al content, as evidenced by collidine adsorption. The number of terminal silanol acid sites was found to be proportional to the external surface area probed by argon sorption experiments. In summary, this work shows that the use of DRIFTS in conjunction with elemental analysis is a valid alternative to qualitatively and quantitatively probe the number and location of hydroxyl acid sites without the use of molar extinction coefficients and gives a comprehensive picture of the effect of Al content on number and location of hydroxyl acid species in ZSM-5 zeolites with varying SAR. The work contributes to advancing the range of characterisation protocols for solid acid catalysts.
The strength of terminal hydroxyl Si-OH groups (silanols) in zeolites is important for many non-size-selective catalytic reactions occurring onto the external surface of the zeolite crystals and may often be responsible for catalyst deactivation, e.g., coke formation. A quantitative analysis of Si-OH strength and its link with the Al content, hence varying silica-to-alumina ratio (SAR = SiO/AlO), has not been established yet. Various hypotheses have been proposed in the literature; nonetheless, the role of Al content in determining silanol strength remains still unclear and the object of speculation. In this work, we have systematically investigated the effect of the Al content on the strength of terminal silanol sites in ZSM-5 zeolite catalysts with varying SAR using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) at variable temperatures without molar extinction coefficients. Two base probe molecules with different proton affinity values, pyridine and collidine, were used. To quantify the strength of terminal silanol sites the change of the terminal silanol peak in the OH stretching region, together with data on elemental analysis, was used. With this experimental protocol, unlike most IR studies, the use of molar extinction coefficients, often difficult to obtain, is not needed for quantification. The results reported here show for the first time that for ZSM-5 zeolite catalysts the fraction of occupied terminal silanol acid sites for both pyridine and collidine increases with increasing concentration of external Brønsted acid sites, hence establishing a clear link between the two types of acid sites. In summary, this work shows that the use of DRIFTS without molar extinction coefficients is able to quantitatively probe the strength of terminal silanol acid sites and establishes a link between the external Brønsted Al content and the strength of terminal silanol species in ZSM-5 zeolites with varying SAR at elevated temperatures.
The relative surface affinities of pyridine within microporous HZSM-5 zeolites are explored using two-dimensional 1H nuclear magnetic resonance (NMR) relaxation time measurements. The dimensionless ratio of longitudinal-to-transverse nuclear spin relaxation...
Terahertz time-domain spectroscopy is used to explore hydrogen bonding structure and dynamics in binary liquid mixtures, spanning a range of protic-protic, protic-aprotic and aprotic-aprotic systems. A direct absorption coefficient analysis is compared against more complex Debye analysis and we observed good agreement of the two methods in determining the hydrogen bonding properties when at least one of the mixture components is protic. When both components are aprotic, we show that the trend in absorption coefficients match well with the theoretical trend in strength of hydrogen bond interactions predicted based on steric and electronic properties of the components.
The Maxwell-Stefan model is a popular diffusion model originally developed to model diffusion of gases, which can be considered thermodynamically ideal mixtures, although its application has been extended to model diffusion in non-ideal liquid mixtures as well. A drawback of the model is that it requires the Maxwell-Stefan diffusion coefficients, which are not based on measurable quantities but they have to be estimated. As a result, numerous estimation methods, such as the Darken model, have been proposed to estimate these diffusion coefficients. However, the Darken model was derived, and is only well defined, for binary systems. This model has been extended to ternary systems according to two proposed forms, one by R. Krishna and J. M. van Baten, Ind. Eng. Chem. Res., 2005, 44, 6939-6947 and the other by X. Liu, T. J. H. Vlugt and A. Bardow, Ind. Eng. Chem. Res., 2011, 50, 10350-10358. In this paper, the two forms have been analysed against the ideal ternary system of methanol/butan-1-ol/propan-1-ol and using experimental values of self-diffusion coefficients. In particular, using pulsed gradient stimulated echo nuclear magnetic resonance (PGSTE-NMR) we have measured the self-diffusion coefficients in various methanol/butan-1-ol/propan-1-ol mixtures. The experimental values of self-diffusion coefficients were then used as the input data required for the Darken model. The predictions of the two proposed multicomponent forms of this model were then compared to experimental values of mutual diffusion coefficients for the ideal alcohol ternary system. This experimental-based approach showed that the Liu's model gives better predictions compared to that of Krishna and van Baten, although it was only accurate to within 26%. Nonetheless, the multicomponent Darken model in conjunction with self-diffusion measurements from PGSTE-NMR represents an attractive method for a rapid estimation of mutual diffusion in multicomponent systems, especially when compared to exhaustive MD simulations.
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