Preparation, Characterization, and Activity of Mono-Dispersed Supported Catalysts
Hicks, Tanya Temaca
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Mono-dispersed supported Ni catalysts were synthesized using the water-CTAB-hexanol reverse micellar system. The core of the reverse micelles contained an aqueous solution of NiCl2. Dynamic light scattering measurements showed that microemulsions having a water-to-surfactant molar ratio, Wo, of 10 lead to reverse micelles with lowest polydispersity, longest stability, and size range of interest. At an oil-to-aqueous phase ratio of 2, the diameter of the reverse micelles was found to increase with Wo in a linear fashion. At higher values of Wo (i.e. 25-30), the polydispersity was found to increase when lowering the amount of surfactant in the system. Ultimately, O/A = 2 and Wo = 10 were chosen as optimal conditions for microemulsion preparation. The aqueous NiCl2 concentration within the micelles was varied between 0.1 and 0.001 M. DLS results showed that although the average micelle diameter was between 70-83 nm throughout the range of metal salt concentrations, the crystallite size estimate based upon the reported micelle diameter and known aqueous NiCl2 concentration ranged between 2 to 7 nm. Therefore, the Ni crystallite size was varied by changing the aqueous NiCl2 concentration due to instability issues arising when changing the value of Wo. After deposition onto an alumina mesh support, the particles were dried, calcined, and reduced to produce Ni clusters. SEM and EDS analysis was used to confirm the presence of Ni compounds after the calcination stage. By the varying the aqueous NiCl2 concentration within the micelles, .0039, .0013, and .00039 wt. % Ni catalysts were produced and characterized using SEM. Particles in the size range of 10-14 nm were noticed for the .0039 wt. % Ni catalysts after reduction, 7-11 nm for .0013 wt. % Ni, and 5-9 nm for .00039 wt. % Ni. The lower-end of these particle size ranges was comparable to the crystallite size estimates. Ethane hydrogenolysis and ethylene hydrogenation reactions were conducted over the emulsion-prepared catalysts in order to determine particle size effects on catalytic activity. Results showed that the catalytic activity, defined in terms of per unit metal surface atom (or TON, turnover number), decreases with increasing particle size for the hydrogenolysis reaction. This trend may be due to an intrinsic size effect in which smaller particles exhibit the chemical or structural properties necessary for achieving a higher reaction rate. The results for ethylene hydrogenation showed that the reaction rate did not significantly change with crystallite size, confirming that the reaction is facile or structure-insensitive.