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Title: Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

Abstract

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts andmore » to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [2];  [3];  [3];  [3];  [3];  [1];  [1];  [4];  [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Illinois Inst. of Technology, Chicago, IL (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division; National Renewable Energy Laboratory (NREL); Illinois Institute of Technology; Purdue University. School of Chemical Engineering
OSTI Identifier:
1362118
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 16; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkane dehydrogenation; EXAFS; XANES; gallium; model compounds; single site catalysts

Citation Formats

Getsoian, Andrew "Bean", Das, Ujjal, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Gallagher, James R., Hu, Bo, Cheah, Singfoong, Schaidle, Joshua A., Ruddy, Daniel A., Hensley, Jesse E., Krause, Theodore R., Curtiss, Larry A., Miller, Jeffrey T., and Hock, Adam S. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES. United States: N. p., 2016. Web. doi:10.1039/c6cy00698a.
Getsoian, Andrew "Bean", Das, Ujjal, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Gallagher, James R., Hu, Bo, Cheah, Singfoong, Schaidle, Joshua A., Ruddy, Daniel A., Hensley, Jesse E., Krause, Theodore R., Curtiss, Larry A., Miller, Jeffrey T., & Hock, Adam S. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES. United States. doi:10.1039/c6cy00698a.
Getsoian, Andrew "Bean", Das, Ujjal, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Gallagher, James R., Hu, Bo, Cheah, Singfoong, Schaidle, Joshua A., Ruddy, Daniel A., Hensley, Jesse E., Krause, Theodore R., Curtiss, Larry A., Miller, Jeffrey T., and Hock, Adam S. Mon . "Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES". United States. doi:10.1039/c6cy00698a. https://www.osti.gov/servlets/purl/1362118.
@article{osti_1362118,
title = {Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES},
author = {Getsoian, Andrew "Bean" and Das, Ujjal and Camacho-Bunquin, Jeffrey and Zhang, Guanghui and Gallagher, James R. and Hu, Bo and Cheah, Singfoong and Schaidle, Joshua A. and Ruddy, Daniel A. and Hensley, Jesse E. and Krause, Theodore R. and Curtiss, Larry A. and Miller, Jeffrey T. and Hock, Adam S.},
abstractNote = {Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.},
doi = {10.1039/c6cy00698a},
journal = {Catalysis Science and Technology},
number = 16,
volume = 6,
place = {United States},
year = {2016},
month = {6}
}

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    journal, January 2019

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    • DOI: 10.1039/c9cp01873e