The reaction of NO and CO on Pt(100) exhibits two branches of steady state production of N2 and CO2 and the occurrence of kinetic oscillations. This system was studied under steady flow conditions in the 10−6 mbar total pressure range using low-energy electron diffraction-(LEED), work function measurement, and mass spectrometry for determination of the reaction rate. These studies revealed that kinetic oscillations can only be initiated from one of the two stable reaction branches. Two separate existence regions were detected in which the oscillations are always damped. Oscillations can be very reproducibly excited by slight decreases in temperature. The 1×1■hex phase transition of the surface structure was observed to take place only in one of the two regions of reaction rate oscillations. Its influence seems to be of minor relevance to the mechanism of oscillations as oscillations in one region occur on the surface that maintains a 1×1 structure. The experiments were modeled by a set of coupled differential equations based on knowledge about the elementary reaction steps. The model calculations reproduced the steady states of the reaction as well as the occurrence of kinetic oscillations in different ranges in excellent agreement with experimental observation. In the model, the phase transition also has no relevance for the oscillation mechanism. The occurrence of oscillations can be rationalized in terms of a periodic sequence of autocatalytic ‘‘surface explosions’’ and the restoration of an adsorbate-covered surface. The damping, experimentally observed, is attributed to insufficient spatial coupling between different regions of the surface.

The main approaches for engineering and healing of defects in zeolites known for their iconic shape-selective properties widely explored in key areas such as catalysis, waste management, gas separation and biomedicine are revealed.

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Rouquerol criterion and the BET equation is in accord with the geometrical surface determined by the chord length distribution method. Therefore BET surface area (S BET) is well representative of micropore surface areas of microporous materials and of total surface area of microporous/mesoporous materials. Mechanical mixtures of mesoporous MCM-41 and microporous FAU-Y powders of known surface areas were used to calculate the respective surface areas by weighted linear combination and the results were compared to the values obtained by the t-plot method. The first slope of the t-plot determined the mesopore + external surface areas (S mes+ext). The linear fit of the first slope is in general in the range 0.01 < p/p 0 < 0.17 and contains the volumes and relative pressures at which all micropores are filled (p/p 0 > 0.10). Overestimation of S mes+ext values was evident and appropriate corrections were provided. External surface areas (S ext) were obtained from the second slope of the t-plot, without noting an overestimation of S ext , thus allowing the determination of mesopore surface areas (S mes) by difference. Micropore surface areas were calculated by subtracting S mes+ext from the total surface area, S BET. As an example, this methodology was applied to the characterization a family of hierarchical microporous/mesoporous FAU-Y (FAUmes) synthesized from H-FAU-Y (H-Y, Si/Al = 15) using C18TAB as surfactant and different NaOH/Si ratio (0.05 < NaOH/Si < 0.25). By increasing the NaOH/Si ratio in synthesis of FAUmes, it was shown that as the micropore surface area decreases, the mesopore surface area increases, while the micropore + mesopore surface area remains constant. This methodology allows accurate characterization of the surface areas of microporous/mesoporous materials.

Flexible small-pore zeolites are interesting candidates for flue and natural gas processing due to their high sorption capacity and selectivity. It is generally accepted that their high CO2/CH4 selectivity is due to cation gating behavior such as the "trapdoor" effect or cation-controlled molecular sieving. Herein, nanosized RHO-type zeolite containing only inorganic cations (Na + and Cs + ) has been prepared from a colloidal precursor suspension at 90 °C for 1 h without the use of expensive organic structure directing agents. The high Cs content significantly improved the thermal stability of the RHO nanocrystals up to 550 °C. The flexibility of the RHO cages upon water adsorption/desorption is demonstrated. The dehydration of the nanosized RHO zeolite resulted in two dehydrated RHO phases, the first one presents an enlargement of the cubic unit cell and a transformation from distorted to the more regular d8r units, and the second one presents a reduction of the cubic unit cell and an increase of the distortion of the d8r units. The 8-rings elliptical distortions of the as synthesized RHO (hydrated form) of 1.87 Å changed to 0.94 Å and 2.16 Å for the two dehydrated RHO forms. The flexibility of the nanosized RHO zeolite is due to the ability of the Cs + cation to displace out from and in to the D8R window sites which is of great importance for controlling the selective adsorption capacity of the RHO zeolite. The flexible RHO-type nanosized zeolite exhibited great selectivity towards CO2 over CH4. The adsorption capacity is retained after 10 cycles of CO2 adsorption/desorption and the crystalline structure is fully preserved.