TY - JOUR
T1 - Isobutane Dehydrogenation over Bulk and Supported Molybdenum Sulfide Catalysts
AU - Cheng, Emily
AU - McCullough, Lauren
AU - Noh, Hyunho
AU - Farha, Omar
AU - Hupp, Joseph
AU - Notestein, Justin
N1 - Funding Information:
This material was based upon work supported by the National Science Foundation Graduate Research Fellowship Grant No. DGE-1324585. This work was also supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0012702. H.N. acknowledges support from the Ryan Fellowship and the Northwestern University International Institute of Nanotechnology (IIN). Abha Gosavi is acknowledged for TEM, and Aaron Peters is acknowledged for providing preliminary materials and helpful discussion. This work made use of the Keck-II and SPID facilities of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the IIN; the Keck Foundation; and the State of Illinois, through the IIN. The metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2020/1/22
Y1 - 2020/1/22
N2 - Bulk and supported MoSx materials have gained interest as alternative catalysts for light alkane dehydrogenation, but there is little kinetic data published with which rigorous comparisons can be made to other catalysts. Here, rates, selectivities, and activation barriers are collected under conditions of differential conversion for the dehydrogenation of isobutane over various morphologies of molybdenum sulfide. We find that a "rag-like" MoS2 composed of small, disordered crystallites exhibits higher catalytic rates than layered, highly crystalline MoS2 (52 vs 2.7 μmol ks-1 gcat -1 at 360 °C). This is in part not only due to increased surface area but also due to intrinsically more active edge and defect sites exposed by the rag-like structure, as shown by a decrease in apparent activation energy from 61 to 43 kJ mol-1. Supporting MoSx on metal oxides or metal organic frameworks gives small MoSx clusters that have up to 7-fold higher rates per mass of MoS2 than even the rag-like MoS2. Rates are support-dependent, with the highest rates per mass of MoS2 observed over MoSx/TiO2. Pt/Al2O3 has a 50-fold higher rate than the best MoS2 catalysts (2700 μmol ks-1 gcat -1 at 360 °C), but it has an apparent activation energy of 41 kJ mol-1, similar to that of the rag-like MoS2. Therefore, the rates over MoS2 appear to be limited by a small number of active sites on the surface, rather than intrinsically poor activity. Given the data provided in this manuscript and the enormous phase space available to metal sulfides, these materials warrant further investigation as alternative light alkane dehydrogenation catalysts, especially for use under conditions that would deactivate a precious metal catalyst.
AB - Bulk and supported MoSx materials have gained interest as alternative catalysts for light alkane dehydrogenation, but there is little kinetic data published with which rigorous comparisons can be made to other catalysts. Here, rates, selectivities, and activation barriers are collected under conditions of differential conversion for the dehydrogenation of isobutane over various morphologies of molybdenum sulfide. We find that a "rag-like" MoS2 composed of small, disordered crystallites exhibits higher catalytic rates than layered, highly crystalline MoS2 (52 vs 2.7 μmol ks-1 gcat -1 at 360 °C). This is in part not only due to increased surface area but also due to intrinsically more active edge and defect sites exposed by the rag-like structure, as shown by a decrease in apparent activation energy from 61 to 43 kJ mol-1. Supporting MoSx on metal oxides or metal organic frameworks gives small MoSx clusters that have up to 7-fold higher rates per mass of MoS2 than even the rag-like MoS2. Rates are support-dependent, with the highest rates per mass of MoS2 observed over MoSx/TiO2. Pt/Al2O3 has a 50-fold higher rate than the best MoS2 catalysts (2700 μmol ks-1 gcat -1 at 360 °C), but it has an apparent activation energy of 41 kJ mol-1, similar to that of the rag-like MoS2. Therefore, the rates over MoS2 appear to be limited by a small number of active sites on the surface, rather than intrinsically poor activity. Given the data provided in this manuscript and the enormous phase space available to metal sulfides, these materials warrant further investigation as alternative light alkane dehydrogenation catalysts, especially for use under conditions that would deactivate a precious metal catalyst.
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U2 - 10.1021/acs.iecr.9b05844
DO - 10.1021/acs.iecr.9b05844
M3 - Article
AN - SCOPUS:85078317781
SN - 0888-5885
VL - 59
SP - 1113
EP - 1122
JO - Industrial and Engineering Chemistry Research
JF - Industrial and Engineering Chemistry Research
IS - 3
ER -