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 »
- Authors:
-
- University of Minnesota-Twin Cities, Minneapolis, MN (United States)
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- 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.
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
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.
@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}
}
Works referenced in this record:
Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr)
journal, July 2013
- Vermoortele, Frederik; Bueken, Bart; Le Bars, Gaëlle
- Journal of the American Chemical Society, Vol. 135, Issue 31
Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo 2 C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation
journal, June 2015
- Lee, Wen-Sheng; Kumar, Anurag; Wang, Zhenshu
- ACS Catalysis, Vol. 5, Issue 7
From fundamentals to applications: a toolbox for robust and multifunctional MOF materials
journal, January 2018
- Kirchon, Angelo; Feng, Liang; Drake, Hannah F.
- Chemical Society Reviews, Vol. 47, Issue 23
Single Ni atoms and Ni4 clusters have similar catalytic activity for ethylene dimerization
journal, October 2017
- Ye, Jingyun; Gagliardi, Laura; Cramer, Christopher J.
- Journal of Catalysis, Vol. 354
Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4 l
journal, January 2017
- Metzger, Eric D.; Comito, Robert J.; Hendon, Christopher H.
- Journal of the American Chemical Society, Vol. 139, Issue 2
Synthesis of the biocompatible and highly stable MIL-127(Fe): from large scale synthesis to particle size control
journal, January 2016
- Chevreau, Hubert; Permyakova, Anastasia; Nouar, Farid
- CrystEngComm, Vol. 18, Issue 22
Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis
journal, December 2017
- Bernales, Varinia; Ortuño, Manuel A.; Truhlar, Donald G.
- ACS Central Science, Vol. 4, Issue 1
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011
- Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
- Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
Structure, characterization, and catalytic properties of open-metal sites in metal organic frameworks
journal, January 2019
- Hall, Jacklyn N.; Bollini, Praveen
- Reaction Chemistry & Engineering, Vol. 4, Issue 2
Probing the correlations between the defects in metal–organic frameworks and their catalytic activity by an epoxide ring-opening reaction
journal, January 2016
- Liu, Yangyang; Klet, Rachel C.; Hupp, Joseph T.
- Chemical Communications, Vol. 52, Issue 50
Propene Oligomerization using Alkali Metal- and Nickel-Exchanged Mesoporous Aluminosilicate Catalysts
journal, December 2013
- Mlinar, Anton N.; Shylesh, Sankaranarayanapillai; Ho, Otto C.
- ACS Catalysis, Vol. 4, Issue 1
Singlet-to-Triplet Spin Transitions Facilitate Selective 1-Butene Formation during Ethylene Dimerization in Ni(II)-MFU-4 l
journal, October 2021
- Mancuso, Jenna L.; Gaggioli, Carlo A.; Gagliardi, Laura
- The Journal of Physical Chemistry C, Vol. 125, Issue 40
Oligomerization of Ethylene to α-Olefins: Discovery and Development of the Shell Higher Olefin Process (SHOP)
journal, October 2013
- Keim, Wilhelm
- Angewandte Chemie International Edition, Vol. 52, Issue 48
Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide
journal, December 2014
- Eubank, Jarrod F.; Wheatley, Paul S.; Lebars, Gaëlle
- APL Materials, Vol. 2, Issue 12
Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst
journal, February 2016
- Metzger, Eric D.; Brozek, Carl K.; Comito, Robert J.
- ACS Central Science, Vol. 2, Issue 3
Origin of highly active metal–organic framework catalysts: defects? Defects!
journal, January 2016
- Canivet, J.; Vandichel, M.; Farrusseng, D.
- Dalton Transactions, Vol. 45, Issue 10
Propene oligomerization over Ni-exchanged Na-X zeolites
journal, December 2012
- Mlinar, Anton N.; Baur, Guillaume B.; Bong, Gerry G.
- Journal of Catalysis, Vol. 296
An X-ray absorption spectroscopy investigation of the coordination environment of electrogenerated Ni( ii )-pseudohalide complexes arising from the anodic polarization of Ni electrodes in DMSO solutions of NCO − , NCS − and NCSe − ions
journal, January 2015
- Alwis, Kethsiri H. K. L.; Ingham, Bridget; Mucalo, Michael R.
- RSC Advances, Vol. 5, Issue 20
Mechanistic insights into alkene chain growth reactions catalyzed by nickel active sites on ordered microporous and mesoporous supports
journal, January 2020
- Joshi, Ravi; Saxena, Arunima; Gounder, Rajamani
- Catalysis Science & Technology, Vol. 10, Issue 21
Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization
journal, October 2016
- Bernales, Varinia; League, Aaron B.; Li, Zhanyong
- The Journal of Physical Chemistry C, Vol. 120, Issue 41
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis
journal, May 2016
- Shearer, Greig C.; Chavan, Sachin; Bordiga, Silvia
- Chemistry of Materials, Vol. 28, Issue 11
Metal-organic framework supported single-site nickel catalysts for butene dimerization
journal, September 2022
- Zheng, Jian; Löbbert, Laura; Chheda, Saumil
- Journal of Catalysis, Vol. 413
Ethene Oligomerization in Ni-Containing Zeolites: Theoretical Discrimination of Reaction Mechanisms
journal, January 2016
- Brogaard, Rasmus Y.; Olsbye, Unni
- ACS Catalysis, Vol. 6, Issue 2
X-ray spectroscopic studies of nickel complexes, with application to the structure of nickel sites in hydrogenases
journal, March 1991
- Colpas, Gerard J.; Maroney, Michael J.; Bagyinka, Csaba.
- Inorganic Chemistry, Vol. 30, Issue 5
The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework
journal, January 2019
- Drake, Hannah F.; Day, Gregory S.; Vali, Shaik Waseem
- Chemical Communications, Vol. 55, Issue 85
Effect of Benzoic Acid as a Modulator in the Structure of UiO-66: An Experimental and Computational Study
journal, April 2017
- Atzori, Cesare; Shearer, Greig C.; Maschio, Lorenzo
- The Journal of Physical Chemistry C, Vol. 121, Issue 17
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012
- Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben
- Angewandte Chemie International Edition, Vol. 51, Issue 20
Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization
journal, April 2018
- Ye, Jingyun; Gagliardi, Laura; Cramer, Christopher J.
- Journal of Catalysis, Vol. 360
Thermal Treatment Effect on CO and NO Adsorption on Fe(II) and Fe(III) Species in Fe 3 O-Based MIL-Type Metal–Organic Frameworks: A Density Functional Theory Study
journal, June 2021
- Vitillo, Jenny G.; Gagliardi, Laura
- Inorganic Chemistry, Vol. 60, Issue 16
Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research
journal, January 2019
- Yang, Dong; Gates, Bruce C.
- ACS Catalysis, Vol. 9, Issue 3
Defects in Metal–Organic Frameworks: Challenge or Opportunity?
journal, August 2015
- Sholl, David S.; Lively, Ryan P.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 17
Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr 6 Nodes of UiO-66 and NU-1000
journal, November 2016
- Yang, Dong; Bernales, Varinia; Islamoglu, Timur
- Journal of the American Chemical Society, Vol. 138, Issue 46
Selective Dimerization of Propylene with Ni-MFU-4 l
journal, April 2017
- Comito, Robert J.; Metzger, Eric D.; Wu, Zhenwei
- Organometallics, Vol. 36, Issue 9
Recent progress of transition metal based catalysts for the selective dimerization of ethylene
journal, July 2018
- Bryliakov, Konstantin P.; Antonov, Artem A.
- Journal of Organometallic Chemistry, Vol. 867
Postsynthesis Annealing of MOF-5 Remarkably Enhances the Framework Structural Stability and CO 2 Uptake
journal, November 2014
- Gadipelli, Srinivas; Guo, Zhengxiao
- Chemistry of Materials, Vol. 26, Issue 22
Selective Ethylene Oligomerization with Chromium-Based Metal–Organic Framework MIL-100 Evacuated under Different Temperatures
journal, January 2017
- Liu, Suyan; Zhang, Ying; Han, Yang
- Organometallics, Vol. 36, Issue 3
Computational Predictions and Experimental Validation of Alkane Oxidative Dehydrogenation by Fe 2 M MOF Nodes
journal, December 2019
- Barona, Melissa; Ahn, Sol; Morris, William
- ACS Catalysis, Vol. 10, Issue 2
Evidence for the Coordination–Insertion Mechanism of Ethene Dimerization at Nickel Cations Exchanged onto Beta Molecular Sieves
journal, October 2018
- Joshi, Ravi; Zhang, Guanghui; Miller, Jeffrey T.
- ACS Catalysis, Vol. 8, Issue 12
Ethene oligomerization on nickel microporous and mesoporous-supported catalysts: Investigation of the active sites
journal, January 2018
- Henry, Reynald; Komurcu, Mustafa; Ganjkhanlou, Yadolah
- Catalysis Today, Vol. 299
Site Densities, Rates, and Mechanism of Stable Ni/UiO-66 Ethylene Oligomerization Catalysts
journal, November 2021
- Yeh, Benjamin; Vicchio, Stephen P.; Chheda, Saumil
- Journal of the American Chemical Society, Vol. 143, Issue 48
Ethylene Oligomerization with Cr−NHC Catalysts: Further Insights into the Extended Metallacycle Mechanism of Chain Growth
journal, August 2008
- McGuinness, David S.; Suttil, James A.; Gardiner, Michael G.
- Organometallics, Vol. 27, Issue 16
Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal–organic frameworks
journal, December 2014
- Feng, Dawei; Wang, Kecheng; Wei, Zhangwen
- Nature Communications, Vol. 5, Issue 1
Stabilization of active, selective, and regenerable Ni-based dimerization catalysts by condensation of ethene withinordered mesopores
journal, August 2017
- Agirrezabal-Telleria, Iker; Iglesia, Enrique
- Journal of Catalysis, Vol. 352
Defect engineering of Mn-based MOFs with rod-shaped building units by organic linker fragmentation
journal, April 2017
- Wu, Doufeng; Yan, Wenqing; Xu, Huoshu
- Inorganica Chimica Acta, Vol. 460
Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework
journal, October 2019
- Simons, Matthew C.; Vitillo, Jenny G.; Babucci, Melike
- Journal of the American Chemical Society, Vol. 141, Issue 45
Beyond upper bound estimates of active site densities in heterogeneous catalysis: A note on the critical role of titrant pressure
journal, September 2022
- Afrin, Sadia; Bollini, Praveen
- Journal of Catalysis, Vol. 413
Beyond Radical Rebound: Methane Oxidation to Methanol Catalyzed by Iron Species in Metal–Organic Framework Nodes
journal, July 2021
- Simons, Matthew C.; Prinslow, Steven D.; Babucci, Melike
- Journal of the American Chemical Society, Vol. 143, Issue 31
Dimerization of Linear Butenes on Zeolite-Supported Ni 2+
journal, November 2018
- Ehrmaier, Andreas; Liu, Yue; Peitz, Stephan
- ACS Catalysis, Vol. 9, Issue 1
Local Structure of CPO-27-Ni Metallorganic Framework upon Dehydration and Coordination of NO
journal, August 2008
- Bonino, Francesca; Chavan, Sachin; Vitillo, Jenny G.
- Chemistry of Materials, Vol. 20, Issue 15
Selective Propene Oligomerization with Nickel(II)-Based Metal–Organic Frameworks
journal, January 2014
- Mlinar, Anton N.; Keitz, Benjamin K.; Gygi, David
- ACS Catalysis, Vol. 4, Issue 3
Beyond the Active Site: Tuning the Activity and Selectivity of a Metal–Organic Framework-Supported Ni Catalyst for Ethylene Dimerization
journal, August 2018
- Liu, Jian; Ye, Jingyun; Li, Zhanyong
- Journal of the American Chemical Society, Vol. 140, Issue 36
Ethene Dimerization on Zeolite-Hosted Ni Ions: Reversible Mobilization of the Active Site
journal, May 2019
- Brogaard, Rasmus Yding; Kømurcu, Mustafa; Dyballa, Michael Martin
- ACS Catalysis, Vol. 9, Issue 6
Mechanistic insights and consequences of intrapore liquids in ethene, propene, and butene dimerization on isolated Ni2+ sites grafted within aluminosilicate mesopores
journal, September 2020
- Agirrezabal-Telleria, Iker; Iglesia, Enrique
- Journal of Catalysis, Vol. 389
Direct accessibility of mixed-metal ( iii / ii ) acid sites through the rational synthesis of porous metal carboxylates
journal, January 2015
- Wongsakulphasatch, S.; Nouar, F.; Rodriguez, J.
- Chemical Communications, Vol. 51, Issue 50
Thermal decarboxylation for the generation of hierarchical porosity in isostructural metal–organic frameworks containing open metal sites
journal, January 2021
- Drake, Hannah F.; Xiao, Zhifeng; Day, Gregory S.
- Materials Advances, Vol. 2, Issue 16