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Title: Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis

Abstract

A mixed-valence oxotrimer metal–organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ~20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ~0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ~62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55–67 kJ mol–1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee–Arlman mechanism for propylene oligomerization through comparisonsmore » between apparent activation energies from steady-state kinetics and computation. Here this study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [2];  [2];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. University of Minnesota-Twin Cities, Minneapolis, MN (United States)
  2. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  3. University of Chicago, IL (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF); National Institutes of Health (NIH)
OSTI Identifier:
1992372
Grant/Contract Number:  
AC02-76SF00515; SC0012702; S10OD011952
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 145; Journal Issue: 6; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysts; hydrocarbons; metal organic frameworks; nickel; oligomerization

Citation Formats

Yeh, Benjamin, Chheda, Saumil, Prinslow, Steven D., Hoffman, Adam S., Hong, Jiyun, Perez-Aguilar, Jorge E., Bare, Simon R., Lu, Connie C., Gagliardi, Laura, and Bhan, Aditya. Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis. United States: N. p., 2023. Web. doi:10.1021/jacs.2c10551.
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Yeh, Benjamin, Chheda, Saumil, Prinslow, Steven D., Hoffman, Adam S., Hong, Jiyun, Perez-Aguilar, Jorge E., Bare, Simon R., Lu, Connie C., Gagliardi, Laura, & Bhan, Aditya. Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis. United States. https://doi.org/10.1021/jacs.2c10551
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Yeh, Benjamin, Chheda, Saumil, Prinslow, Steven D., Hoffman, Adam S., Hong, Jiyun, Perez-Aguilar, Jorge E., Bare, Simon R., Lu, Connie C., Gagliardi, Laura, and Bhan, Aditya. Wed . "Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis". United States. https://doi.org/10.1021/jacs.2c10551. https://www.osti.gov/servlets/purl/1992372.
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@article{osti_1992372,
title = {Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis},
author = {Yeh, Benjamin and Chheda, Saumil and Prinslow, Steven D. and Hoffman, Adam S. and Hong, Jiyun and Perez-Aguilar, Jorge E. and Bare, Simon R. and Lu, Connie C. and Gagliardi, Laura and Bhan, Aditya},
abstractNote = {A mixed-valence oxotrimer metal–organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ~20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ~0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ~62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55–67 kJ mol–1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee–Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. Here this study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.},
doi = {10.1021/jacs.2c10551},
journal = {Journal of the American Chemical Society},
number = 6,
volume = 145,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2023},
month = {Wed Feb 01 00:00:00 EST 2023}
}
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