Tuesday, October 1, 2013

Nanoscale 3D Imaging and Quantification of Pt/Zeolite Y Hydrocracking Catalysts

CATEGORY: ZEOLITES
23rd North American Catalysis Society Meeting, June 2-7, 2013, Louisville, Kentucky
Nanoscale 3D Imaging and Quantification of Pt/Zeolite Y Hydrocracking Catalysts
Jovana Zečević
k.p.dejong@uu.nl
1 Inorganic Chemistry and Catalysis,Utrecht University, Utrecht (The Netherlands) 1, Heiner Friedrich2, Petra E. de Jongh1 and Krijn P. de Jong1*
2 Materials and Interface Chemistry, Eindhoven University of Technology, Eindhoven (The Netherlands)
Introduction
A wide range of important industrial processes rely heavily on supported metal catalysts, such as bi-functional zeolite supported Pt catalyst used in oil refineries for hydrocracking and hydroisomerisation. Assessing particle size distribution and their location within zeolite support is crucial for understanding the reaction mechanisms as well as for improving catalyst design. Commonly used bulk techniques, such as EXAFS, NMR, H2-chemisorption provide only the average size of Pt particles, while TEM is the most direct technique which enables visualization of Pt particles and manual measurement which is often biased, labor intensive and susceptible to errors. Therefore, authors used electron tomography (3D-TEM)  coupled with image processing for a detailed, nanoscale, qualitative and quantitative study of industrially relevant Pt-zeolite Y catalyst.
Results and Discussion
Optimum imaging conditions enabled us for the first time to visualize and locate in 3D thousands of Pt particles as small as 1 nm. Image analysis of 3D reconstructions provided semi-automated measurement of valuable morphological properties inaccessible to other techniques and facilitated comparison of the impact of preparation procedures  on particle sizes, particle locations and particle-particle distances. In all of the analyzed crystals prepared by incipient wetness impregnation (IWI) and common heat treatments, the Pt size distribution was narrow with a mean diameter of 1.0 - 1.3 nm, which is close to the size of zeolite Y micropore cavities. Careful observation of the reconstructed volumes suggests that most of the Pt particles were located inside the microporous crystalline regions, even when their size exceeded the size of the micropore cavity. Thus, Pt particles are assumed to grow to 1.2 – 3 nm diameter on the account of local destruction of the zeolite Y lattice. To confirm this finding, impregnated zeolite was submitted to direct reduction in H2 to promote Pt growth. The majority of Pt particles were found to be still residing within microporous regions even though they are larger than zeolite Y micropore cavities. This phenomenon has been suggested in an earlier study , however, imaged here for the first time. Surprisingly, a homogeneous distribution of Pt particles was observed in all of the imaged zeolite crystals, however, the calculated Pt loading varied among crystals from 0.2 to 7.1 wt% (Fig 1b). Interestingly, the variation in Pt loading does not seem to influence size distribution of Pt particles, pointing to their pronounced stability within micropore cavities.
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