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(575d) 2D Surface Structures in Microporous Catalysts

Dauenhauer, P., University of Minnesota
Conner, W. C., University of Massachusetts
Qi, X., University of Massachusetts Amherst
Mountziaris, T. J., University of Massachusetts
Fan, W., University of Massachusetts Amherst

Zeolites are used to catalyze chemical reactions and improve selectivity to desired products through well ordered, shape selective microporous channels. MFI-structured ZSM-5 has widely been used for catalytic conversion biomass.[1] To maximize turnover frequencies, microporous and mesoporous materials are now being synthesized with length scales approaching that of a single lattice (pillared, nanosheets, membranes, etc.). However, in small particles, mass transfer becomes dominant and the apparent diffusivity appears to be orders of magnitude smaller than through large particles.[23] This has led to the general phenomenon referred to as 'surface barriers,' which describes the hindrance to mass transfer at the surface of zeolite catalyst particles. While this timescale is often negligible when compared to the diffusion or reaction times, we show that it does contribute significantly to overall turnover in small particles.[2,4] Chemical species exhibiting differing kinetic diameters and adsorption affinities were used to probe diffusion within MFI-structured zeolites to elucidate the role of guest molecule size and binding energy. Kinetic Monte Carlo simulations are used to mechanistically probe the effect of physical structures on overall transport timescales, including internal grain boundaries, regular surface restrictions and total pore blockages. The relative trends with particle size are compared to experimental measurements and potential mechanisms are proposed.

1. Williams, C. L.; Chang, C.-C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J., Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene. ACS Catalysis 2012, 2, (6), 935-939.

2. Teixeira, A. R.; Chang, C.-C.; Coogan, T.; Kendall, R.; Fan, W.; Dauenhauer, P. J., Dominance of Surface Barriers in Molecular Transport through Silicalite-1. The Journal of Physical Chemistry C 2013,117, (48), 25545-25555.

3.   Chang, C.-C.; Teixeira, A. R.; Li, C.; Dauenhauer, P. J.; Fan, W., Enhanced Molecular Transport in Hierarchical Silicalite-1. Langmuir 2013, 29, (45), 13943-13950.

4. A.R. Teixeira, X. Qi, C. Chang, W. Fan, W.C. Conner, P.J. Dauenhauer, “On Asymmetric Surface Barriers in MFI Zeolite Revealed by Frequency Response,” J. Phys. Chem. C. 2014, 118(38), 22166.