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Title: A Mesoporous Cobalt Aluminate Spinel Catalyst for Nonoxidative Propane Dehydrogenation

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1]; ORCiD logo [1]
  1. School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr. Atlanta GA 30332 USA
  2. Engineering & Process Sciences, The Dow Chemical Company, Freeport TX 77541 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1390855
Resource Type:
Journal Article
Resource Relation:
Journal Name: ChemCatChem; Journal Volume: 9; Journal Issue: 17
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Hu, Bo, Kim, Wun-Gwi, Sulmonetti, Taylor P., Sarazen, Michele L., Tan, Shuai, So, Jungseob, Liu, Yujun, Dixit, Ravindra S., Nair, Sankar, and Jones, Christopher W.. A Mesoporous Cobalt Aluminate Spinel Catalyst for Nonoxidative Propane Dehydrogenation. United States: N. p., 2017. Web. doi:10.1002/cctc.201700647.
Hu, Bo, Kim, Wun-Gwi, Sulmonetti, Taylor P., Sarazen, Michele L., Tan, Shuai, So, Jungseob, Liu, Yujun, Dixit, Ravindra S., Nair, Sankar, & Jones, Christopher W.. A Mesoporous Cobalt Aluminate Spinel Catalyst for Nonoxidative Propane Dehydrogenation. United States. doi:10.1002/cctc.201700647.
Hu, Bo, Kim, Wun-Gwi, Sulmonetti, Taylor P., Sarazen, Michele L., Tan, Shuai, So, Jungseob, Liu, Yujun, Dixit, Ravindra S., Nair, Sankar, and Jones, Christopher W.. 2017. "A Mesoporous Cobalt Aluminate Spinel Catalyst for Nonoxidative Propane Dehydrogenation". United States. doi:10.1002/cctc.201700647.
@article{osti_1390855,
title = {A Mesoporous Cobalt Aluminate Spinel Catalyst for Nonoxidative Propane Dehydrogenation},
author = {Hu, Bo and Kim, Wun-Gwi and Sulmonetti, Taylor P. and Sarazen, Michele L. and Tan, Shuai and So, Jungseob and Liu, Yujun and Dixit, Ravindra S. and Nair, Sankar and Jones, Christopher W.},
abstractNote = {},
doi = {10.1002/cctc.201700647},
journal = {ChemCatChem},
number = 17,
volume = 9,
place = {United States},
year = 2017,
month = 8
}
  • The oxidative dehydrogenation of propane to propene was investigated over a series of novel vanadia-based catalysts supported on high-surface-area magnesium spinel. A mesoporous MgAl2O4 support was synthesized via a low-temperature sol gel process involving the heterobimetallic alkoxide precursor, Mg[Al(O iPr)4]2. A high-purity catalyst support was obtained after calcination at 1173 K under O2 atmosphere and active vanadia catalysts were prepared from the thermolysis of OV(O tBu)3 after grafting onto the spinel support. MgAl2O4-supported catalysts prepared in this manner have BET surface areas of 234 245 m2/g. All of the catalysts were characterized by X-ray powder diffraction, and Raman, solid-state NMR,more » and diffuse-reflectance UV vis spectroscopy. At all vanadium loadings the vanadia supported on MgAl2O4 exist as a combination of isolated monovanadate and tetrahedral polyvanadate species. As the vanadium surface density increases for these catalysts the ratio of polyvanadate species to isolated monovanadate species increases. In addition, as the vanadium surface density increases for these catalysts, the initial rate of propane ODH per V atom increases and reaches a maximum value at 6 VOx/nm2. Increasing the vanadium surface density past this point results in a decrease in the rate of propane ODH owing to the formation of multilayer species in which subsurface vanadium atoms are essentially rendered catalytically inactive. The initial propene selectivity increases with increasing vanadium surface density and reaches a plateau of {approx}95 percent for the V/MgAl catalysts. Rate coefficients for propane ODH (k1), propane combustion (k2), and propene combustion (k3) were calculated for these catalysts. The value of k1 increases with increasing VOx surface density, reaching a maximum at about 5.5 VOx/nm2. On the other hand, the ratio (k2/k1) for V/MgAl decreases with increasing VOx surface density. The ratio (k3/k1) for both sets of catalysts shows no dependence on the vanadia surface density. The observed trends in k1, (k2/k1), and (k3/k1) are discussed in terms of the surface structure of the catalyst.« less
  • The oxidative dehydrogenation of propane to propene was investigated over a series of novel vanadia-based catalysts supported on high-surface-area magnesium spinel. A mesoporous MgAl2O4 support was synthesized via a low-temperature sol gel process involving the heterobimetallic alkoxide precursor, Mg[Al(O iPr)4]2. A high-purity catalyst support was obtained after calcination at 1173 K under O2 atmosphere and active vanadia catalysts were prepared from the thermolysis of OV(O tBu)3 after grafting onto the spinel support. MgAl2O4-supported catalysts prepared in this manner have BET surface areas of 234 245 m2/g. All of the catalysts were characterized by X-ray powder diffraction, and Raman, solid-state NMR,more » and diffuse-reflectance UV vis spectroscopy. At all vanadium loadings the vanadia supported on MgAl2O4 exist as a combination of isolated monovanadate and tetrahedral polyvanadate species. As the vanadium surface density increases for these catalysts the ratio of polyvanadate species to isolated monovanadate species increases. In addition, as the vanadium surface density increases for these catalysts, the initial rate of propane ODH per V atom increases and reaches a maximum value at 6 VOx/nm2. Increasing the vanadium surface density past this point results in a decrease in the rate of propane ODH owing to the formation of multilayer species in which subsurface vanadium atoms are essentially rendered catalytically inactive. The initial propene selectivity increases with increasing vanadium surface density and reaches a plateau of {approx}95 percent for the V/MgAl catalysts. Rate coefficients for propane ODH (k1), propane combustion (k2), and propene combustion (k3) were calculated for these catalysts. The value of k1 increases with increasing VOx surface density, reaching a maximum at about 5.5 VOx/nm2. On the other hand, the ratio (k2/k1) for V/MgAl decreases with increasing VOx surface density. The ratio (k3/k1) for both sets of catalysts shows no dependence on the vanadia surface density. The observed trends in k1, (k2/k1), and (k3/k1) are discussed in terms of the surface structure of the catalyst.« less
  • This paper reports on a systematic X-ray diffraction study that was undertaken to characterize the stoichiometric spinel (MgAl{sub 2}O{sub 4}), alumina excess spinel (MgAl{sub 2}O{sub 4} {center dot} xAl{sub 2}O{sub 3}) and magnesia excess spinel (MgAl{sub 2}O{sub 4} {center dot} MgO). A Vegard's plot, lattice parameter vs the composition of these solid solutions, reveals that, in alumina excess spinel, a continuous solid solution (x = 0 {minus} {infinity}) exists, while, in magnesia excess material, the solid solution is limited to y = 0-1. When y = 1, a solid solution assumes the composition of MgAl{sub 2}O{sub 4} {center dot} MgO.more » If y {gt} 1, both periclase and stoichiometric spinel (MgAl{sub 2}O{sub 4}) phases coexist. The SO{sub x} removal activity of various hydrothermally stable cerium oxide containing solid solution spinels was evaluated. In the magnesia excess solid solutions, SO{sub x} removal activity increased as MgO increased and reached maximum at y = 1, which is the CeO{sub 2}/MgAl{sub 2}O{sub 4} {center dot} MgO system. This catalyst is the most widely used SO{sub x} reduction catalyst today.« less
  • Here, Zr-based metal–organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr 6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in themore » two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O 2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.« less
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