A series of univalent cation forms of zeolite Rho (M(9.8)Al(9.8)Si(38.2)O(96), M = H, Li, Na, K, NH(4), Cs) and ultrastabilized zeolite Rho (US-Rho) have been prepared. Their CO(2) adsorption behavior has been measured at 298 K and up to 1 bar and related to the structures of the dehydrated forms determined by Rietveld refinement and, for H-Rho and US-Rho, by solid state NMR. Additionally, CO(2) adsorption properties of the H-form of the silicoalumino-phosphate with the RHO topology and univalent cation forms of the zeolite ZK-5 were measured for comparison. The highest uptakes at 0.1 bar, 298 K for both Rho and ZK-5 were obtained on the Li-forms (Li-Rho, 3.4 mmol g(-1); Li-ZK-5, 4.7 mmol g(-1)). H- and US-Rho had relatively low uptakes under these conditions: extra-framework Al species do not interact strongly with CO(2). Forms of zeolite Rho in which cations occupy window sites between α-cages show hysteresis in their CO(2) isotherms, the magnitude of which (Na(+),NH(4)(+) < K(+) < Cs(+)) correlates with the tendency for cations to occupy double eight-membered ring sites rather than single eight-membered ring sites. Hysteresis is not observed for zeolites where cations do not occupy the intercage windows. In situ synchrotron X-ray diffraction of the CO(2) adsorption on Na-Rho at 298 K identifies the adsorption sites. The framework structure of Na-Rho "breathes" as CO(2) is adsorbed and desorbed and its desorption kinetics from Na-Rho at 308 K have been quantified by the Zero Length Column chromatographic technique. Na-Rho shows much higher CO(2)/C(2)H(6) selectivity than Na-ZK-5, as determined by single component adsorption, indicating that whereas CO(2) can diffuse readily through windows containing Na(+) cations, ethane cannot.

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Hydrated niobium oxides are used as strong solid acids with a wide variety of catalytic applications, yet the correlations between structure and acidity remain unclear. New insights into the structural features giving rise to Lewis and Brønsted acid sites are presently achieved. It appears that Lewis acid sites can arise from lower coordinate NbO and in some cases NbO sites, which are due to the formation of oxygen vacancies in thin and flexible NbO systems. Such structural flexibility of Nb-O systems is particularly pronounced in high surface area nanostructured materials, including few-layer to monolayer or mesoporous NbO·nHO synthesized in the presence of stabilizers. Bulk materials on the other hand only possess a few acid sites due to lower surface areas and structural rigidity: small numbers of Brønsted acid sites on HNbO arise from a protonic structure due to the water content, whereas no acid sites are detected for anhydrous crystalline H-NbO.

The present work addresses the aggregation/dispersion properties of two commercial titanias for application as photocatalysts in concrete technology. A microsized m‐TiO2 (average particle size 153.7 ± 48.1 nm) and a nanosized n‐TiO2 (average particle size 18.4 ± 5.0 nm) have been tested in different ionic media (Na+, K+, Ca2+, Cl−, SO42−, synthetic cement pore solution) at different pHs and in real cement paste specimens. Results highlighted that ion–ion correlations play a fundamental role in TiO2 particles aggregation in the cement environment. A particle aggregation model derived from TiO2 surface chemistry is proposed here and used to justify such aggregation phenomena in real cement paste. Scanning electron microscopy–energy‐dispersive X‐ray spectroscopic investigations on hardened cement specimens completely confirmed the qualitative model based on titania surface chemistry. Experimental results also show how size and nature of TiO2 aggregates dramatically influence the overall photocatalytic activity of cementitious materials containing TiO2.

Pd doped Cu catalysts have been prepared by co-impregnation, sequential impregnation and a colloidal approach. In each case, the Cu : Pd ratio was optimised leading to catalyst activity which exceeded that offered by monometallic Cu at low temperature (393 K and below) but with a product selectivity which suggests the reaction is still taking place on a Cu surface (i.e., high ethylene selectivity). Pd is therefore thought to influence hydrogen dissociation rates and enhance spillover onto Cu sites. Catalytic testing under more demanding conditions showed differences between the preparation methods. In general, the most active of the samples appeared to be the least selective and vice-versa. Under optimised conditions, a 50 : 1 Cu : Pd ratio prepared by sequential impregnation showed an ethylene selectivity of 80% at 98% conversion at only 353 K. Further testing under competitive conditions suggested good ethylene selectivity could be retained under industrially relevant conditions in the absence of CO.