Diffusion and reaction in pore hierarchies by the two-region model

The two-region (“Kärger”) model of diffusion in complex pore spaces is exploited for quantitating mass transfer in hierarchically organized nanoporous materials, consisting of a continuous microporous bulk phase permeated by a network of transport pores. With the implications that the diffusivity in the transport pores significantly exceeds the diffusivity in the micropores and that the relative population of the transport pores is far below that of the micropores, overall transport depends on only three independent parameters. Depending on their interrelation, enhancement of the overall mass transfer is found to be ensured by two fundamentally different mechanisms. They are referred to as the limiting cases of fast and slow exchange, with the respective time constants of molecular uptake being controlled by different parameters. Complemented with reaction terms, the two-region model may equally successfully be applied to the quantitation of the combined effect of diffusion and reaction in terms of the effectiveness factor. Generalization of the classical Thiele concept is shown to provide an excellent estimate of the effectiveness factor of a chemical reaction in hierarchically porous materials, solely based on the intrinsic reaction rate and the time constant of molecular uptake relevant to the given conditions.

Diagnosing surface versus bulk reactivity for molecular catalysis within metal–organic frameworks using a quantitative kinetic model

This report presents diagnostic criteria for determining the limiting processes of MOF-based catalysis: either mass/charge transport or the intrinsic reaction rate. This will facilitate future catalytic material design.

Influence of the Anatase/Rutile Ratio on the TiO2 Photocatalytic Activity for the Photodegradation of Light Hydrocarbons

A set of TiO2 samples with different anatase/rutile ratios was prepared by calcinations at different temperatures from commercial photocatalyst Degussa P25. The effects of the two crystalline phases of titanium (IV) oxide on the photocatalytic activity in gaseous phase through oxidation of light hydrocarbons were studied. Crystalline phase transformation from anatase to rutile occurred at 700°C for P25. Results indicate that samples with higher anatase/rutile ratios presented higher intrinsic activities for the photodegradation of a propane/isobutane/butane (40/35/25 %V) mixture. However, the activity did not totally disappear after complete crystalline transformation from anatase to rutile, indicating that the pure rutile phase also presents photoactivity. During the photocatalytic reaction of TiO2 samples, a linear dependence was found between the inverse of the intrinsic reaction rate constant (k intrinsic) and the water adsorption capacity in the surface (WAPS) of the synthesized TiO2 catalyst. The thermal treatment used to induce the formation of rutile by calcination would presumably reduce water adsorption capacity and surface area, leading to a decrease in photocatalytic activity.