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

Mandal, Mukunda; Cramer, Christopher J.; Truhlar, Donald G.; Sauer, Joachim; Gagliardi, Laura

doi:10.1021/acscatal.0c02300

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

Journal Article · Thu Aug 06 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02300· OSTI ID:1721719

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Univ. of Minnesota, Minneapolis, MN (United States); University of Minnesota
Univ. of Minnesota, Minneapolis, MN (United States)
Humboldt-Univ. zu Berlin (Germany)

Single-site catalysts with active species anchored over metal–organic framework (MOF) supports have garnered significant interest in recent years. Catalysts with vanadium oxide (VO_x) 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 VO_x-incorporated MOF catalysts (V-MOF) by employing density functional theory. Based on the mode of VO_x 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012702

OSTI ID:: 1721719

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 17 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

Single-Site Heterogeneous Catalysts Thomas, John Meurig; Raja, Robert; Lewis, Dewi W. Angewandte Chemie International Edition, Vol. 44, Issue 40, p. 6456-6482 https://doi.org/10.1002/anie.200462473	journal	October 2005
Stabilized Vanadium Catalyst for Olefin Polymerization by Site Isolation in a Metal–Organic Framework Comito, Robert J.; Wu, Zhenwei; Zhang, Guanghui Angewandte Chemie International Edition, Vol. 57, Issue 27 https://doi.org/10.1002/anie.201803642	journal	July 2018
cPCET versus HAT: A Direct Theoretical Method for Distinguishing X-H Bond-Activation Mechanisms Klein, Johannes E. M. N.; Knizia, Gerald Angewandte Chemie International Edition, Vol. 57, Issue 37 https://doi.org/10.1002/anie.201805511	journal	August 2018
Stabilizing a Vanadium Oxide Catalyst by Supporting on a Metal-Organic Framework Cui, Yuexing; Rimoldi, Martino; Platero-Prats, Ana E. ChemCatChem, Vol. 10, Issue 8 https://doi.org/10.1002/cctc.201701658	journal	February 2018
Differentiation of mono-oxo and polyoxo and of monomeric and polymeric vanadate, molybdate and tungstate species in metal oxide catalysts by IR and Raman spectroscopy Busca, Guido Journal of Raman Spectroscopy, Vol. 33, Issue 5 https://doi.org/10.1002/jrs.867	journal	January 2002
Extended Hartree-Fock (EHF) theory of chemical reactions: III. Projected M�ller-Plesset (PMP) perturbation wavefunctions for transition structures of organic reactions Yamaguchi, K.; Takahara, Y.; Fueno, T. Theoretica Chimica Acta, Vol. 73, Issue 5-6 https://doi.org/10.1007/bf00527740	journal	January 1988
Energy-adjustedab initio pseudopotentials for the second and third row transition elements Andrae, D.; H�u�ermann, U.; Dolg, M. Theoretica Chimica Acta, Vol. 77, Issue 2 https://doi.org/10.1007/bf01114537	journal	January 1990
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts Wasson, Megan C.; Buru, Cassandra T.; Chen, Zhijie Applied Catalysis A: General, Vol. 586 https://doi.org/10.1016/j.apcata.2019.117214	journal	September 2019
Efficient oxidative dehydrogenation of ethanol by VOx@MIL-101: On par with VOx/ZrO2 and much better than MIL-47(V) Bulánek, Roman; Čičmanec, Pavel; Kotera, Jiří Catalysis Today, Vol. 324 https://doi.org/10.1016/j.cattod.2018.07.034	journal	March 2019
A new model for the molecular structure of supported vanadium oxide catalysts Gijzeman, Onno L. J.; van Lingen, Joost N. J.; van Lenthe, Joop H. Chemical Physics Letters, Vol. 397, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.09.001	journal	October 2004
Vibrational spectra of alumina- and silica-supported vanadia revisited: An experimental and theoretical model catalyst study Magg, N. Journal of Catalysis, Vol. 226, Issue 1 https://doi.org/10.1016/j.jcat.2004.04.021	journal	August 2004
Oxidative dehydrogenation of propane: Differences between N2O and O2 in the reoxidation of reduced vanadia sites and consequences for selectivity Rozanska, X.; Kondratenko, E.; Sauer, J. Journal of Catalysis, Vol. 256, Issue 1 https://doi.org/10.1016/j.jcat.2008.03.002	journal	May 2008
Partial oxidation of ethanol on vanadia catalysts on supporting oxides with different redox properties compared to propane Beck, Benjamin; Harth, Manuel; Hamilton, Neil G. Journal of Catalysis, Vol. 296 https://doi.org/10.1016/j.jcat.2012.09.008	journal	December 2012
Metal-organic frameworks as emerging platform for supporting isolated single-site catalysts Zhao, Wenshi; Li, Guodong; Tang, Zhiyong Nano Today, Vol. 27 https://doi.org/10.1016/j.nantod.2019.05.007	journal	August 2019
Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study Keller, Daphne E.; Visser, Tom; Soulimani, Fouad Vibrational Spectroscopy, Vol. 43, Issue 1 https://doi.org/10.1016/j.vibspec.2006.07.005	journal	January 2007
Electronic Structure Modeling of Metal–Organic Frameworks Mancuso, Jenna L.; Mroz, Austin M.; Le, Khoa N. Chemical Reviews, Vol. 120, Issue 16 https://doi.org/10.1021/acs.chemrev.0c00148	journal	July 2020
Catalytic Applications of Vanadium: A Mechanistic Perspective Langeslay, Ryan R.; Kaphan, David M.; Marshall, Christopher L. Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00245	journal	October 2018
Metal–Organic Framework-Based Catalysts with Single Metal Sites Wei, Yong-Sheng; Zhang, Mei; Zou, Ruqiang Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00757	journal	May 2020
Carboxylate Structural Effects on the Properties and Proton-Coupled Electron Transfer Reactivity of [CuO ₂ CR] ²⁺ Cores Elwell, Courtney E.; Mandal, Mukunda; Bouchey, Caitlin J. Inorganic Chemistry, Vol. 58, Issue 23 https://doi.org/10.1021/acs.inorgchem.9b02293	journal	November 2019
Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks Otake, Ken-ichi; Ye, Jingyun; Mandal, Mukunda ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b01043	journal	April 2019
Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis Bernales, Varinia; Ortuño, Manuel A.; Truhlar, Donald G. ACS Central Science, Vol. 4, Issue 1 https://doi.org/10.1021/acscentsci.7b00500	journal	December 2017
Marine haloperoxidases Butler, Alison.; Walker, J. V. Chemical Reviews, Vol. 93, Issue 5 https://doi.org/10.1021/cr00021a014	journal	July 1993
Vanadium-Node-Functionalized UiO-66: A Thermally Stable MOF-Supported Catalyst for the Gas-Phase Oxidative Dehydrogenation of Cyclohexene Nguyen, Huong Giang T.; Schweitzer, Neil M.; Chang, Chih-Yi ACS Catalysis, Vol. 4, Issue 8, p. 2496-2500 https://doi.org/10.1021/cs5001448	journal	June 2014
Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries Alecu, I. M.; Zheng, Jingjing; Zhao, Yan Journal of Chemical Theory and Computation, Vol. 6, Issue 9 https://doi.org/10.1021/ct100326h	journal	August 2010
Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts Knizia, Gerald Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400687b	journal	October 2013
Metal–Organic Frameworks of Vanadium as Catalysts for Conversion of Methane to Acetic Acid Phan, Anh; Czaja, Alexander U.; Gándara, Felipe Inorganic Chemistry, Vol. 50, Issue 16, p. 7388-7390 https://doi.org/10.1021/ic201396m	journal	August 2011
Synthesis and Reactivity of Oxo-Peroxo-Vanadium(V) Bipyridine Compounds Waidmann, Christopher R.; DiPasquale, Antonio G.; Mayer, James M. Inorganic Chemistry, Vol. 49, Issue 5 https://doi.org/10.1021/ic9022618	journal	January 2010
Oxidation of Methanol to Formaldehyde on Supported Vanadium Oxide Catalysts Compared to Gas Phase Molecules Döbler, Jens; Pritzsche, Marc; Sauer, Joachim Journal of the American Chemical Society, Vol. 127, Issue 31 https://doi.org/10.1021/ja051720e	journal	August 2005
Presence of Surface Vanadium Peroxo-oxo Umbrella Structures in Supported Vanadium Oxide Catalysts: Fact or Fiction? Molinari, Julie E.; Wachs, Israel E. Journal of the American Chemical Society, Vol. 132, Issue 36 https://doi.org/10.1021/ja105392g	journal	September 2010
Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/Ceria Kropp, Thomas; Paier, Joachim; Sauer, Joachim Journal of the American Chemical Society, Vol. 136, Issue 41 https://doi.org/10.1021/ja508657c	journal	October 2014
Perturbing the Copper(III)–Hydroxide Unit through Ligand Structural Variation Dhar, Debanjan; Yee, Gereon M.; Spaeth, Andrew D. Journal of the American Chemical Society, Vol. 138, Issue 1 https://doi.org/10.1021/jacs.5b10985	journal	December 2015
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 Yang, Dong; Bernales, Varinia; Islamoglu, Timur Journal of the American Chemical Society, Vol. 138, Issue 46 https://doi.org/10.1021/jacs.6b08273	journal	November 2016
Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal–Organic Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship Otake, Ken-ichi; Cui, Yuexing; Buru, Cassandra T. Journal of the American Chemical Society, Vol. 140, Issue 28 https://doi.org/10.1021/jacs.8b05107	journal	June 2018
Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal–Organic Frameworks for Alcohol Oxidation Wang, Xingjie; Zhang, Xuan; Li, Peng Journal of the American Chemical Society https://doi.org/10.1021/jacs.9b02603	journal	May 2019
Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer? Mandal, Mukunda; Elwell, Courtney E.; Bouchey, Caitlin J. Journal of the American Chemical Society, Vol. 141, Issue 43 https://doi.org/10.1021/jacs.9b08109	journal	October 2019
In Situ Raman Spectroscopy of Supported Transition Metal Oxide Catalysts: ¹⁸ O ₂ − ¹⁶ O ₂ Isotopic Labeling Studies Weckhuysen, Bert M.; Jehng, Jih-Mirn; Wachs, Israel E. The Journal of Physical Chemistry B, Vol. 104, Issue 31 https://doi.org/10.1021/jp000055n	journal	August 2000
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 Ovsitser, Olga; Cherian, Maymol; Kondratenko, Evgenii V. The Journal of Physical Chemistry C, Vol. 111, Issue 24 https://doi.org/10.1021/jp070747c	journal	June 2007
A Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Isolated Vanadate Species Supported on Silica Goodrow, Anthony; Bell, Alexis T. The Journal of Physical Chemistry C, Vol. 111, Issue 40 https://doi.org/10.1021/jp072627a	journal	October 2007
Catalytically Active Vanadia Species on Silica: Effect of Oxygen and Water Sauer, Joachim; Pritzsche, Marc; Döbler, Jens The Journal of Physical Chemistry C, Vol. 118, Issue 50 https://doi.org/10.1021/jp505114t	journal	July 2014
Frequency and Zero-Point Vibrational Energy Scale Factors for Double-Hybrid Density Functionals (and Other Selected Methods): Can Anharmonic Force Fields Be Avoided? Kesharwani, Manoj K.; Brauer, Brina; Martin, Jan M. L. The Journal of Physical Chemistry A, Vol. 119, Issue 9 https://doi.org/10.1021/jp508422u	journal	September 2014
Vanadia and Water Coadsorption on Tetragonal Zirconia Surfaces Hofmann, Alexander; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim The Journal of Physical Chemistry C, Vol. 113, Issue 42 https://doi.org/10.1021/jp902755e	journal	September 2009
Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Vanadium Oxide Species Supported on Silica: Umbrella Model Ding, Xun-Lei; Xue, Wei; Ma, Yan-Ping The Journal of Physical Chemistry C, Vol. 114, Issue 7 https://doi.org/10.1021/jp9112415	journal	February 2010
Defining the Proton Topology of the Zr₆-Based Metal–Organic Framework NU-1000 Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723 https://doi.org/10.1021/jz501899j	journal	October 2014
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Supported vanadium oxide in heterogeneous catalysis: elucidating the structure–activity relationship with spectroscopy Muylaert, Ilke; Van Der Voort, Pascal Physical Chemistry Chemical Physics, Vol. 11, Issue 16 https://doi.org/10.1039/b819808j	journal	January 2009
Vanadium metal–organic frameworks: structures and applications Van Der Voort, Pascal; Leus, Karen; Liu, Ying-Ya New J. Chem., Vol. 38, Issue 5 https://doi.org/10.1039/c3nj01130e	journal	January 2014
The concept, reality and utility of single-site heterogeneous catalysts (SSHCs) Thomas, John Meurig Phys. Chem. Chem. Phys., Vol. 16, Issue 17 https://doi.org/10.1039/c4cp00513a	journal	January 2014
Vanadium bromoperoxidase (VBrPO) mimics: synthesis, structure and a comparative account of the catalytic activity of newly synthesized oxidovanadium and oxido-peroxidovanadium complexes Palmajumder, Eshita; Patra, Swarup; Drew, Michael G. B. New Journal of Chemistry, Vol. 40, Issue 10 https://doi.org/10.1039/c6nj00767h	journal	January 2016
Metal–organic and covalent organic frameworks as single-site catalysts Rogge, S. M. J.; Bavykina, A.; Hajek, J. Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/c7cs00033b	journal	January 2017
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
Rational design of single-site heterogeneous catalysts: towards high chemo-, regio- and stereoselectivity Dal Santo, Vladimiro; Guidotti, Matteo; Psaro, Rinaldo Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 468, Issue 2143 https://doi.org/10.1098/rspa.2012.0056	journal	March 2012

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

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