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Title: Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation [Introducing Nonstructural Ligands to Zirconia-like MOF Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation]

Abstract

Previous work has shown that introduction of hexafluoroacetylacetone (Facac) units as nonstructural ligands for the zirconia-like nodes of the eight-connected metal-organic framework (MOF), NU-1000, greatly alters the selectivity of node-supported oxy-nickel clusters for ethylene dimerization vs oligomerization. Here we i explore a related concept: tuning of support/catalyst interactions, and therefore, catalyst activity, via parallel installation of organic modifiers on the support itself. As modifiers we focused on para-substituted benzoates (R-BA; R = -NH2, -OCH3, -CH3, -H, -F, and -NO2) where the substituents were chosen to present similar steric demand, but varying electron-donating or electron-withdrawing properties. R-benzoate-engendered shifts in the node-based aqua O-H stretching frequency for NU-1000, as measured by DRIFTS (diffuse-reflectance infrared Fourier-transform spectroscopy), together with systematic shifts in Ni 2p peak energies, as measured by X-ray photoelectron spectroscopy, show that the electronic properties of the support can be modulated. The vibrational and electronic peak shifts correlate with the putative electron-withdrawing vs electron-donating strength of the para-substituted benzoate modifiers. Subsequent installation of node-supported, oxy-Ni(II) clusters for ethylene hydrogenation yield a compelling correlation between log (catalyst turnover frequency) and the electron donating or withdrawing character of the substituent of the benzoate units. Single crystal X-ray diffraction measurements reveal that each organicmore » modifier makes use of only one of two available carboxylate oxygens to accomplish grafting. The remaining oxygen atom is, in principle, well positioned to coordinate directly to an installed Ni(II) ion. We postulate that the unanticipated direct coordination of the catalyst by the node-modifier (rather than indirect modifier-based tuning of support(node)/catalyst electronic interactions) is the primary source of the observed systematic tuning of hydrogenation activity. Here we suggest, however, that regardless of mechanism for communication with active-sites of MOF-supported catalysts, intentional elaboration of nodes via grafted, nonstructural organic species could prove to be a valuable general strategy for fine-tuning supported-catalyst activity and/or selectivity.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of New South Wales, Sydney, NSW (Australia)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1509897
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hammett constant; ethylene hydrogenation; heterogeneous catalysis; ligand modification; metal-organic framework; zirconia-like node

Citation Formats

Liu, Jian, Li, Zhanyong, Zhang, Xuan, Otake, Ken-ichi, Zhang, Lin, Peters, Aaron W., Young, Matthias J., Bedford, Nicholas M., Letourneau, Steven P., Mandia, David J., Elam, Jeffrey W., Farha, Omar K., and Hupp, Joseph T. Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation [Introducing Nonstructural Ligands to Zirconia-like MOF Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation]. United States: N. p., 2019. Web. doi:10.1021/acscatal.8b04828.
Liu, Jian, Li, Zhanyong, Zhang, Xuan, Otake, Ken-ichi, Zhang, Lin, Peters, Aaron W., Young, Matthias J., Bedford, Nicholas M., Letourneau, Steven P., Mandia, David J., Elam, Jeffrey W., Farha, Omar K., & Hupp, Joseph T. Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation [Introducing Nonstructural Ligands to Zirconia-like MOF Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation]. United States. https://doi.org/10.1021/acscatal.8b04828
Liu, Jian, Li, Zhanyong, Zhang, Xuan, Otake, Ken-ichi, Zhang, Lin, Peters, Aaron W., Young, Matthias J., Bedford, Nicholas M., Letourneau, Steven P., Mandia, David J., Elam, Jeffrey W., Farha, Omar K., and Hupp, Joseph T. 2019. "Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation [Introducing Nonstructural Ligands to Zirconia-like MOF Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation]". United States. https://doi.org/10.1021/acscatal.8b04828. https://www.osti.gov/servlets/purl/1509897.
@article{osti_1509897,
title = {Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation [Introducing Nonstructural Ligands to Zirconia-like MOF Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation]},
author = {Liu, Jian and Li, Zhanyong and Zhang, Xuan and Otake, Ken-ichi and Zhang, Lin and Peters, Aaron W. and Young, Matthias J. and Bedford, Nicholas M. and Letourneau, Steven P. and Mandia, David J. and Elam, Jeffrey W. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Previous work has shown that introduction of hexafluoroacetylacetone (Facac) units as nonstructural ligands for the zirconia-like nodes of the eight-connected metal-organic framework (MOF), NU-1000, greatly alters the selectivity of node-supported oxy-nickel clusters for ethylene dimerization vs oligomerization. Here we i explore a related concept: tuning of support/catalyst interactions, and therefore, catalyst activity, via parallel installation of organic modifiers on the support itself. As modifiers we focused on para-substituted benzoates (R-BA–; R = -NH2, -OCH3, -CH3, -H, -F, and -NO2) where the substituents were chosen to present similar steric demand, but varying electron-donating or electron-withdrawing properties. R-benzoate-engendered shifts in the node-based aqua O-H stretching frequency for NU-1000, as measured by DRIFTS (diffuse-reflectance infrared Fourier-transform spectroscopy), together with systematic shifts in Ni 2p peak energies, as measured by X-ray photoelectron spectroscopy, show that the electronic properties of the support can be modulated. The vibrational and electronic peak shifts correlate with the putative electron-withdrawing vs electron-donating strength of the para-substituted benzoate modifiers. Subsequent installation of node-supported, oxy-Ni(II) clusters for ethylene hydrogenation yield a compelling correlation between log (catalyst turnover frequency) and the electron donating or withdrawing character of the substituent of the benzoate units. Single crystal X-ray diffraction measurements reveal that each organic modifier makes use of only one of two available carboxylate oxygens to accomplish grafting. The remaining oxygen atom is, in principle, well positioned to coordinate directly to an installed Ni(II) ion. We postulate that the unanticipated direct coordination of the catalyst by the node-modifier (rather than indirect modifier-based tuning of support(node)/catalyst electronic interactions) is the primary source of the observed systematic tuning of hydrogenation activity. Here we suggest, however, that regardless of mechanism for communication with active-sites of MOF-supported catalysts, intentional elaboration of nodes via grafted, nonstructural organic species could prove to be a valuable general strategy for fine-tuning supported-catalyst activity and/or selectivity.},
doi = {10.1021/acscatal.8b04828},
url = {https://www.osti.gov/biblio/1509897}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 4,
volume = 9,
place = {United States},
year = {Fri Mar 01 00:00:00 EST 2019},
month = {Fri Mar 01 00:00:00 EST 2019}
}

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Works referenced in this record:

A history of industrial catalysis
journal, April 2011


How fracking is upending the chemical industry
journal, October 2017


Catalytic control of emissions from cars
journal, April 2011


Atomic layer deposition of Pt@CsH2PO4 for the cathodes of solid acid fuel cells
journal, October 2018


The Rise of Hydrogen Peroxide as the Main Product by Metal‐Free Catalysis in Oxygen Reductions
journal, August 2018


Highly Selective Nonoxidative Coupling of Methane over Pt-Bi Bimetallic Catalysts
journal, February 2018


Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017


Pd/Cu-Oxide Nanoconjugate at Zeolite-Y Crystallite Crafting the Mesoporous Channels for Selective Oxidation of Benzyl-Alcohols
journal, September 2017


Viewpoint on the Partial Oxidation of Methane to Methanol Using Cu- and Fe-Exchanged Zeolites
journal, August 2018


Ethene oligomerization on nickel microporous and mesoporous-supported catalysts: Investigation of the active sites
journal, January 2018


Identifying Zeolite Topologies for Storage and Release of Hydrogen
journal, May 2018


Reticular Chemistry—Construction, Properties, and Precision Reactions of Frameworks
journal, November 2016


Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials
journal, August 2013


Introduction to Metal–Organic Frameworks
journal, September 2011


Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF
journal, September 2016


Soft porous crystals
journal, November 2009


Zeolite-like metal–organic frameworks (ZMOFs): design, synthesis, and properties
journal, January 2015


Hybrid porous solids past, present, future
journal, January 2008


A facile synthesis of UiO-66, UiO-67 and their derivatives
journal, January 2013


Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks
journal, June 2012


Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination
journal, October 2013


A Series of Highly Stable Mesoporous Metalloporphyrin Fe-MOFs
journal, August 2014


Nanoscale Metal–Organic Framework for Highly Effective Photodynamic Therapy of Resistant Head and Neck Cancer
journal, November 2014


Metal–Organic Frameworks for Heterogeneous Basic Catalysis
journal, May 2017


Stabilized Vanadium Catalyst for Olefin Polymerization by Site Isolation in a Metal–Organic Framework
journal, July 2018


Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks
journal, December 2017


CO 2 Hydrogenation over Pt-Containing UiO-67 Zr-MOFs—The Base Case
journal, June 2017


Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis
journal, December 2017


Electrospun metal–organic framework polymer composites for the catalytic degradation of methyl paraoxon
journal, January 2017


Titration of Zr3(μ-OH) Hydroxy Groups at the Cornerstones of Bulk MOF UiO-67, [Zr6O4(OH)4(biphenyldicarboxylate)6], and Their Reaction with [AuMe(PMe3)]
journal, May 2012


Stable Metal-Organic Frameworks: Design, Synthesis, and Applications
journal, February 2018


Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000
journal, October 2014


Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology
journal, November 2013


Zr- and Hf-Based Metal–Organic Frameworks: Tracking Down the Polymorphism
journal, February 2013


MOF Functionalization via Solvent-Assisted Ligand Incorporation: Phosphonates vs Carboxylates
journal, February 2015


Electroactive Ferrocene at or near the Surface of Metal–Organic Framework UiO-66
journal, March 2018


Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework
journal, February 2016


Stable Metal–Organic Framework-Supported Niobium Catalysts
journal, October 2016


Toward Inexpensive Photocatalytic Hydrogen Evolution: A Nickel Sulfide Catalyst Supported on a High-Stability Metal–Organic Framework
journal, August 2016


Stabilizing a Vanadium Oxide Catalyst by Supporting on a Metal-Organic Framework
journal, February 2018


Fine-Tuning the Activity of Metal–Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane
journal, October 2017


Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015


Increased Electrical Conductivity in a Mesoporous Metal–Organic Framework Featuring Metallacarboranes Guests
journal, February 2018


The role of redox hopping in metal–organic framework electrocatalysis
journal, January 2018


A MOF platform for incorporation of complementary organic motifs for CO 2 binding
journal, January 2015


Detoxification of a Sulfur Mustard Simulant Using a BODIPY-Functionalized Zirconium-Based Metal–Organic Framework
journal, July 2017


Understanding light-driven H 2 evolution through the electronic tuning of aminopyridine cobalt complexes
journal, January 2018


Transition metal catalysis in confined spaces
journal, January 2015


Enhancing the catalytic activity of hydronium ions through constrained environments
journal, March 2017


Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production
journal, April 2012


Hydrogen Generation by Hangman Metalloporphyrins
journal, June 2011


Electric Fields and Enzyme Catalysis
journal, June 2017


Heterogeneous catalysis: The importance of interfacial interactions
journal, March 2018


Size and Promoter Effects on Stability of Carbon-Nanofiber-Supported Iron-Based Fischer–Tropsch Catalysts
journal, May 2016


Heterogeneous Catalysis: A Central Science for a Sustainable Future
journal, March 2017


Tuning Nickel with Lewis Acidic Group 13 Metalloligands for Catalytic Olefin Hydrogenation
journal, September 2015


Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E -Alkenes
journal, October 2018


Structural Assessment and Catalytic Consequences of the Oxygen Coordination Environment in Grafted Ti−Calixarenes
journal, February 2007


Beyond the Active Site: Tuning the Activity and Selectivity of a Metal–Organic Framework-Supported Ni Catalyst for Ethylene Dimerization
journal, August 2018


Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
journal, October 2013

  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804
  • https://doi.org/10.1021/ja408959g

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires
journal, July 2017


Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands
journal, October 2011


Works referencing / citing this record:

Heterometallic multinuclear nodes directing MOF electronic behavior
journal, January 2020