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Title: Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks

Abstract

Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VOx) species immobilized over Zr-NU-1000 and Hf-MOF-808 (which have nodes containing six Zr(IV) or Hf(IV) ions, respectively) were recently characterized experimentally and were reported to be active for the selective oxidation of benzyl alcohol to benzaldehyde. Here, we report a detailed computational investigation of these VOx-incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VOx attachment, various structures are explored, and their relative stabilities and computed IR spectral features are reported. Mechanisms for the selective oxidation reaction are investigated. The analysis of electron flow in the turnover-limiting C–H activation step shows that the hydrogen-atom abstraction process involves a concerted proton-coupled electron-transfer mechanism. Here, the results of this study suggest that in addition to the identity of the metal in the node, the MOF node architecture plays a crucial role in driving the catalytic activities of V-MOFs.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Humboldt-Univ. zu Berlin (Germany)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1721719
Grant/Contract Number:  
SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 10; Journal Issue: 17; 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; DFT modeling; metal−organic framework; single-site catalyst; vanadium; proton-coupled electron transfer; alcohols; metal organic frameworks; chemical structure; catalysts; molecular structure

Citation Formats

Mandal, Mukunda, Cramer, Christopher J., Truhlar, Donald G., Sauer, Joachim, and Gagliardi, Laura. Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks. United States: N. p., 2020. Web. doi:10.1021/acscatal.0c02300.
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Mandal, Mukunda, Cramer, Christopher J., Truhlar, Donald G., Sauer, Joachim, & Gagliardi, Laura. Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks. United States. https://doi.org/10.1021/acscatal.0c02300
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Mandal, Mukunda, Cramer, Christopher J., Truhlar, Donald G., Sauer, Joachim, and Gagliardi, Laura. Thu . "Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks". United States. https://doi.org/10.1021/acscatal.0c02300. https://www.osti.gov/servlets/purl/1721719.
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@article{osti_1721719,
title = {Structure and Reactivity of Single-Site Vanadium Catalysts Supported on Metal–Organic Frameworks},
author = {Mandal, Mukunda and Cramer, Christopher J. and Truhlar, Donald G. and Sauer, Joachim and Gagliardi, Laura},
abstractNote = {Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VOx) species immobilized over Zr-NU-1000 and Hf-MOF-808 (which have nodes containing six Zr(IV) or Hf(IV) ions, respectively) were recently characterized experimentally and were reported to be active for the selective oxidation of benzyl alcohol to benzaldehyde. Here, we report a detailed computational investigation of these VOx-incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VOx attachment, various structures are explored, and their relative stabilities and computed IR spectral features are reported. Mechanisms for the selective oxidation reaction are investigated. The analysis of electron flow in the turnover-limiting C–H activation step shows that the hydrogen-atom abstraction process involves a concerted proton-coupled electron-transfer mechanism. Here, the results of this study suggest that in addition to the identity of the metal in the node, the MOF node architecture plays a crucial role in driving the catalytic activities of V-MOFs.},
doi = {10.1021/acscatal.0c02300},
journal = {ACS Catalysis},
number = 17,
volume = 10,
place = {United States},
year = {Thu Aug 06 00:00:00 EDT 2020},
month = {Thu Aug 06 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acscatal.0c02300
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Works referenced in this record:

Metal-organic frameworks as emerging platform for supporting isolated single-site catalysts
journal, August 2019

Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts
journal, September 2019

Metal–Organic Framework-Based Catalysts with Single Metal Sites
journal, May 2020

Single-Site Heterogeneous Catalysts
journal, October 2005

  • Thomas, John Meurig; Raja, Robert; Lewis, Dewi W.
  • Angewandte Chemie International Edition, Vol. 44, Issue 40, p. 6456-6482
  • DOI: 10.1002/anie.200462473

Rational design of single-site heterogeneous catalysts: towards high chemo-, regio- and stereoselectivity
journal, March 2012

  • Dal Santo, Vladimiro; Guidotti, Matteo; Psaro, Rinaldo
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 468, Issue 2143
  • DOI: 10.1098/rspa.2012.0056

Supported vanadium oxide in heterogeneous catalysis: elucidating the structure–activity relationship with spectroscopy
journal, January 2009

  • Muylaert, Ilke; Van Der Voort, Pascal
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 16
  • DOI: 10.1039/b819808j

Catalytic Applications of Vanadium: A Mechanistic Perspective
journal, October 2018

Partial oxidation of ethanol on vanadia catalysts on supporting oxides with different redox properties compared to propane
journal, December 2012

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

  • Cui, Yuexing; Rimoldi, Martino; Platero-Prats, Ana E.
  • ChemCatChem, Vol. 10, Issue 8
  • DOI: 10.1002/cctc.201701658

The concept, reality and utility of single-site heterogeneous catalysts (SSHCs)
journal, January 2014

Electronic Structure Modeling of Metal–Organic Frameworks
journal, July 2020

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

Vanadium-Node-Functionalized UiO-66: A Thermally Stable MOF-Supported Catalyst for the Gas-Phase Oxidative Dehydrogenation of Cyclohexene
journal, June 2014

  • Nguyen, Huong Giang T.; Schweitzer, Neil M.; Chang, Chih-Yi
  • ACS Catalysis, Vol. 4, Issue 8, p. 2496-2500
  • DOI: 10.1021/cs5001448

Metal–Organic Frameworks of Vanadium as Catalysts for Conversion of Methane to Acetic Acid
journal, August 2011

  • Phan, Anh; Czaja, Alexander U.; Gándara, Felipe
  • Inorganic Chemistry, Vol. 50, Issue 16, p. 7388-7390
  • DOI: 10.1021/ic201396m

Efficient oxidative dehydrogenation of ethanol by VOx@MIL-101: On par with VOx/ZrO2 and much better than MIL-47(V)
journal, March 2019

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

  • Comito, Robert J.; Wu, Zhenwei; Zhang, Guanghui
  • Angewandte Chemie International Edition, Vol. 57, Issue 27
  • DOI: 10.1002/anie.201803642

Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal–Organic Frameworks for Alcohol Oxidation
journal, May 2019

  • Wang, Xingjie; Zhang, Xuan; Li, Peng
  • Journal of the American Chemical Society
  • DOI: 10.1021/jacs.9b02603

Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal–Organic Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship
journal, June 2018

  • Otake, Ken-ichi; Cui, Yuexing; Buru, Cassandra T.
  • Journal of the American Chemical Society, Vol. 140, Issue 28
  • DOI: 10.1021/jacs.8b05107

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

  • Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723
  • DOI: 10.1021/jz501899j

Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks
journal, April 2019

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries
journal, August 2010

  • Alecu, I. M.; Zheng, Jingjing; Zhao, Yan
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 9
  • DOI: 10.1021/ct100326h

Frequency and Zero-Point Vibrational Energy Scale Factors for Double-Hybrid Density Functionals (and Other Selected Methods): Can Anharmonic Force Fields Be Avoided?
journal, September 2014

  • Kesharwani, Manoj K.; Brauer, Brina; Martin, Jan M. L.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 9
  • DOI: 10.1021/jp508422u

Oxidation of Methanol to Formaldehyde on Supported Vanadium Oxide Catalysts Compared to Gas Phase Molecules
journal, August 2005

  • Döbler, Jens; Pritzsche, Marc; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 127, Issue 31
  • DOI: 10.1021/ja051720e

Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/Ceria
journal, October 2014

  • Kropp, Thomas; Paier, Joachim; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja508657c

Perturbing the Copper(III)–Hydroxide Unit through Ligand Structural Variation
journal, December 2015

  • Dhar, Debanjan; Yee, Gereon M.; Spaeth, Andrew D.
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b10985

Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study
journal, January 2007

Vanadia and Water Coadsorption on Tetragonal Zirconia Surfaces
journal, September 2009

  • Hofmann, Alexander; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim
  • The Journal of Physical Chemistry C, Vol. 113, Issue 42
  • DOI: 10.1021/jp902755e

Catalytically Active Vanadia Species on Silica: Effect of Oxygen and Water
journal, July 2014

  • Sauer, Joachim; Pritzsche, Marc; Döbler, Jens
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp505114t

In Situ Raman Spectroscopy of Supported Transition Metal Oxide Catalysts:  18 O 2 − 16 O 2 Isotopic Labeling Studies
journal, August 2000

  • Weckhuysen, Bert M.; Jehng, Jih-Mirn; Wachs, Israel E.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 31
  • DOI: 10.1021/jp000055n

A new model for the molecular structure of supported vanadium oxide catalysts
journal, October 2004

  • Gijzeman, Onno L. J.; van Lingen, Joost N. J.; van Lenthe, Joop H.
  • Chemical Physics Letters, Vol. 397, Issue 1-3
  • DOI: 10.1016/j.cplett.2004.09.001

Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Vanadium Oxide Species Supported on Silica: Umbrella Model
journal, February 2010

  • Ding, Xun-Lei; Xue, Wei; Ma, Yan-Ping
  • The Journal of Physical Chemistry C, Vol. 114, Issue 7
  • DOI: 10.1021/jp9112415

Marine haloperoxidases
journal, July 1993

Synthesis and Reactivity of Oxo-Peroxo-Vanadium(V) Bipyridine Compounds
journal, January 2010

  • Waidmann, Christopher R.; DiPasquale, Antonio G.; Mayer, James M.
  • Inorganic Chemistry, Vol. 49, Issue 5
  • DOI: 10.1021/ic9022618

Presence of Surface Vanadium Peroxo-oxo Umbrella Structures in Supported Vanadium Oxide Catalysts: Fact or Fiction?
journal, September 2010

  • Molinari, Julie E.; Wachs, Israel E.
  • Journal of the American Chemical Society, Vol. 132, Issue 36
  • DOI: 10.1021/ja105392g

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
  • DOI: 10.1021/jacs.6b08273

A Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Isolated Vanadate Species Supported on Silica
journal, October 2007

  • Goodrow, Anthony; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 40
  • DOI: 10.1021/jp072627a

Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?
journal, October 2019

  • Mandal, Mukunda; Elwell, Courtney E.; Bouchey, Caitlin J.
  • Journal of the American Chemical Society, Vol. 141, Issue 43
  • DOI: 10.1021/jacs.9b08109

Carboxylate Structural Effects on the Properties and Proton-Coupled Electron Transfer Reactivity of [CuO 2 CR] 2+ Cores
journal, November 2019

In-Situ UV/vis and Transient Isotopic Analysis of the Role of Oxidizing Agent in the Oxidative Dehydrogenation of Propane over Silica-Supported Vanadia Catalysts
journal, June 2007

  • Ovsitser, Olga; Cherian, Maymol; Kondratenko, Evgenii V.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 24
  • DOI: 10.1021/jp070747c

Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts
journal, October 2013

  • Knizia, Gerald
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 11
  • DOI: 10.1021/ct400687b

cPCET versus HAT: A Direct Theoretical Method for Distinguishing X-H Bond-Activation Mechanisms
journal, August 2018

  • Klein, Johannes E. M. N.; Knizia, Gerald
  • Angewandte Chemie International Edition, Vol. 57, Issue 37
  • DOI: 10.1002/anie.201805511
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