Computational Investigation of the Role of Active Site Heterogeneity for aSupported Organovanadium(III) Hydrogenation Catalyst

Patel, Prajay; Wells, Robert H.; Kaphan, David M.; Delferro, Massimiliano; Skodje, Rex T.; Liu, Cong

doi:10.1021/acscatal.1c00688

Computational Investigation of the Role of Active Site Heterogeneity for aSupported Organovanadium(III) Hydrogenation Catalyst

Journal Article · Fri Jun 18 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c00688· OSTI ID:1845827

Patel, Prajay ^[1]; Wells, Robert H. ^[2]; Kaphan, David M. ^[1]; Delferro, Massimiliano ^[1]; Skodje, Rex T. ^[2]; Liu, Cong ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Colorado, Boulder, CO (United States)

A crucial consideration for supported heterogeneous catalysts is the nonuniformity of the active sites, particularly for supported organometallic catalysts. Standard spectroscopic techniques, such as X-ray absorption spectroscopy, reflect the nature of the most populated sites, which are often intrinsically structurally distinct from the most active catalytic sites. Additionally, with computational models, often, only a few representative structures are used to depict catalytic active sites on a surface, even though there are numerous observable factors of surface heterogeneity that contribute to the kinetically favorable active species. A previously reported study on the mechanism of a surface organovanadium-(III) catalyst [(SiO₂)V^III(Mes)(THF)] for styrene hydrogenation yielded two possible mechanisms: heterolytic cleavage and redox cycling. These two mechanistic scenarios are challenging to differentiate experimentally since the kinetic readouts of the catalyst are identical. To showcase the importance of modeling surface heterogeneity and its effect on catalytic activity, density functional theory (DFT) computational models of a series of potential active sites of [(SiO₂)V^III(Mes)(THF)] for the reaction pathways are applied in combination with kinetic Monte Carlo (kMC) simulations. Computed results were then compared to the previously reported experimental kinetic study: (1) DFT free-energy reaction pathways indicated the likely active site and pathway for styrene hydrogenation, a heterolytic cleavage pathway requiring a bare tripodal vanadium site. (2) From the kMC simulations, a mixture of different bond lengths from the support oxygen to the metal center was required to qualitatively describe the experimentally observed kinetic aspects of a supported organovanadium(III) catalyst for olefin hydrogenation. This work underscores the importance of modeling surface heterogeneity in computational catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1845827

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

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
Metal‐Surface Interactions and Surface Heterogeneity in ‘Well‐Defined’ Silica‐Supported Alkene Metathesis Catalysts: Evidences and Consequences Pucino, Margherita; Liao, Wei‐Chih; Chan, Ka Wing Helvetica Chimica Acta, Vol. 103, Issue 6 https://doi.org/10.1002/hlca.202000072	journal	June 2020
Characterization of amorphous silica based catalysts using DFT computational methods Tielens, Frederik; Gierada, Maciej; Handzlik, Jarosław Catalysis Today, Vol. 354 https://doi.org/10.1016/j.cattod.2019.03.062	journal	September 2020
On silsesquioxanes’ accuracy as molecular models for silica-grafted complexes in heterogeneous catalysis Quadrelli, Elsje Alessandra; Basset, Jean-Marie Coordination Chemistry Reviews, Vol. 254, Issue 5-6 https://doi.org/10.1016/j.ccr.2009.09.031	journal	March 2010
Catalytic sites in silica-supported titanium catalysts: silsesquioxane complexes as models Fraile, J.; Garcia, J.; Mayoral, J. Journal of Catalysis, Vol. 233, Issue 1 https://doi.org/10.1016/j.jcat.2005.04.018	journal	July 2005
Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica Liu, Cong; Camacho-Bunquin, Jeffrey; Ferrandon, Magali Polyhedron, Vol. 152 https://doi.org/10.1016/j.poly.2018.06.006	journal	September 2018
Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts Pelletier, Jérémie D. A.; Basset, Jean-Marie Accounts of Chemical Research, Vol. 49, Issue 4 https://doi.org/10.1021/acs.accounts.5b00518	journal	March 2016
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities Copéret, Christophe; Comas-Vives, Aleix; Conley, Matthew P. Chemical Reviews, Vol. 116, Issue 2 https://doi.org/10.1021/acs.chemrev.5b00373	journal	January 2016
Strain in Silica-Supported Ga(III) Sites: Neither Too Much nor Too Little for Propane Dehydrogenation Catalytic Activity Praveen, C. S.; Borosy, A. P.; Copéret, C. Inorganic Chemistry, Vol. 60, Issue 10 https://doi.org/10.1021/acs.inorgchem.0c03135	journal	February 2021
Hydrogen Activation by Silica-Supported Metal Ion Catalysts: Catalytic Properties of Metals and Performance of DFT Functionals Plascencia, Cesar; Curtiss, Larry A.; Liu, Cong The Journal of Physical Chemistry A, Vol. 123, Issue 1 https://doi.org/10.1021/acs.jpca.8b08340	journal	December 2018
Ethanol Decomposition on Pd–Au Alloy Catalysts Li, Hao; Evans, Edward J.; Mullins, C. Buddie The Journal of Physical Chemistry C, Vol. 122, Issue 38 https://doi.org/10.1021/acs.jpcc.8b08150	journal	August 2018
Understanding Surface Catalyzed Decomposition Reactions Using a Chemical Pathway Analysis Wells, Robert H.; Gu, Xiang-Kui; Li, Wei-Xue The Journal of Physical Chemistry C, Vol. 122, Issue 49 https://doi.org/10.1021/acs.jpcc.8b09415	journal	November 2018
Nontraditional Catalyst Supports in Surface Organometallic Chemistry Witzke, Ryan J.; Chapovetsky, Alon; Conley, Matthew P. ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c03350	journal	September 2020
Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from Density Functional Theory (DFT) Studies Das, Ujjal; Zhang, Guanghui; Hu, Bo ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01699	journal	November 2015
Tantalum–Polyhedral Oligosilsesquioxane Complexes as Structural Models and Functional Catalysts for Epoxidation Guillo, Pascal; Lipschutz, Michael I.; Fasulo, Meg E. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00020	journal	February 2017
Beyond Ordered Materials: Understanding Catalytic Sites on Amorphous Solids Goldsmith, Bryan R.; Peters, Baron; Johnson, J. Karl ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b01767	journal	October 2017
Analogy between Enzyme and Nanoparticle Catalysis: A Single-Molecule Perspective Ye, Rong; Mao, Xianwen; Sun, Xiangcheng ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04926	journal	January 2019
Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation Kaphan, David M.; Ferrandon, Magali S.; Langeslay, Ryan R. ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b02800	journal	November 2019
Kinetic Monte Carlo Simulations Unveil Synergic Effects at Work on Bifunctional Catalysts Prats, Hèctor; Posada-Pérez, Sergio; Rodriguez, José A. ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02813	journal	August 2019
First-Principles Analysis of Structure Sensitivity in NO Oxidation on Pt Bray, J. M.; Schneider, W. F. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501783q	journal	January 2015
On Surface Heterogeneity and Catalytic Kinetics Murzin, Dmitry Yu. Industrial & Engineering Chemistry Research, Vol. 44, Issue 6 https://doi.org/10.1021/ie049044x	journal	February 2005
Silsesquioxanes as models for silica surfaces Feher, Frank J.; Newman, David A.; Walzer, John F. Journal of the American Chemical Society, Vol. 111, Issue 5 https://doi.org/10.1021/ja00187a028	journal	March 1989
Molecular Understanding of the Formation of Surface Zirconium Hydrides upon Thermal Treatment under Hydrogen of [(⋮SiO)Zr(CH ₂ t Bu) ₃ ] by Using Advanced Solid-State NMR Techniques Rataboul, Franck; Baudouin, Anne; Thieuleux, Chloé Journal of the American Chemical Society, Vol. 126, Issue 39 https://doi.org/10.1021/ja038486h	journal	October 2004
First-Principles-Based Kinetic Monte Carlo Simulation of the Structure Sensitivity of the Water–Gas Shift Reaction on Platinum Surfaces Stamatakis, Michail; Chen, Ying; Vlachos, Dionisios G. The Journal of Physical Chemistry C, Vol. 115, Issue 50 https://doi.org/10.1021/jp2071869	journal	November 2011
Combined Density Functional Theory and Kinetic Monte Carlo Study of Selective Oxidation of NH ₃ on Rutile RuO ₂ (110) at Ambient Pressures Shah, Syed Islamuddin; Hong, Sampyo; Rahman, Talat S. The Journal of Physical Chemistry C, Vol. 118, Issue 10 https://doi.org/10.1021/jp407865e	journal	February 2014
Structure of Fe–N _x –C Defects in Oxygen Reduction Reaction Catalysts from First-Principles Modeling Holby, Edward F.; Wu, Gang; Zelenay, Piotr The Journal of Physical Chemistry C, Vol. 118, Issue 26 https://doi.org/10.1021/jp503266h	journal	June 2014
Characterization of Supported Vanadium Oxide Species on Silica: A Periodic DFT Investigation Islam, Mazharul M.; Costa, Dominique; Calatayud, Monica The Journal of Physical Chemistry C, Vol. 113, Issue 24 https://doi.org/10.1021/jp902818m	journal	May 2009
Sum over Histories Representation for Chemical Kinetics Bai, Shirong; Zhou, Dingyu; Davis, Michael J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 1 https://doi.org/10.1021/jz502239v	journal	December 2014
Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics Xu, Weilin; Kong, Jason S.; Yeh, Yun-Ting E. Nature Materials, Vol. 7, Issue 12 https://doi.org/10.1038/nmat2319	journal	November 2008
Site-averaged kinetics for catalysts on amorphous supports: an importance learning algorithm Vandervelden, Craig; Khan, Salman Ahmad; Scott, Susannah L. Reaction Chemistry & Engineering https://doi.org/10.1039/C9RE00356H	journal	January 2019
Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression Khan, Salman A.; Vandervelden, Craig A.; Scott, Susannah L. Reaction Chemistry & Engineering https://doi.org/10.1039/C9RE00357F	journal	January 2020
Silica-supported single-site catalysts: to be or not to be? A conjecture on silica surfaces Gajan, David; Copéret, Christophe New Journal of Chemistry, Vol. 35, Issue 11 https://doi.org/10.1039/c1nj20506d	journal	January 2011
Gas phase metal cluster model systems for heterogeneous catalysis Lang, Sandra M.; Bernhardt, Thorsten M. Physical Chemistry Chemical Physics, Vol. 14, Issue 26 https://doi.org/10.1039/c2cp40660h	journal	January 2012
Isolated, well-defined organovanadium( iii ) on silica: single-site catalyst for hydrogenation of alkenes and alkynes Sohn, H.; Camacho-Bunquin, J.; Langeslay, R. R. Chemical Communications, Vol. 53, Issue 53 https://doi.org/10.1039/c7cc01876b	journal	January 2017
Surface organometallic chemistry in heterogeneous catalysis Samantaray, Manoja K.; Pump, Eva; Bendjeriou-Sedjerari, Anissa Chemical Society Reviews, Vol. 47, Issue 22 https://doi.org/10.1039/c8cs00356d	journal	January 2018
Compact effective potentials and efficient shared‐exponent basis sets for the first‐ and second‐row atoms Stevens, Walter J.; Basch, Harold; Krauss, Morris The Journal of Chemical Physics, Vol. 81, Issue 12 https://doi.org/10.1063/1.447604	journal	December 1984
Effective core potential methods for the lanthanides Cundari, Thomas R.; Stevens, Walter J. The Journal of Chemical Physics, Vol. 98, Issue 7 https://doi.org/10.1063/1.464902	journal	April 1993
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
Single atom catalysts on amorphous supports: A quenched disorder perspective Peters, Baron; Scott, Susannah L. The Journal of Chemical Physics, Vol. 142, Issue 10 https://doi.org/10.1063/1.4914145	journal	March 2015
Assessment of mean-field microkinetic models for CO methanation on stepped metal surfaces using accelerated kinetic Monte Carlo Andersen, Mie; Plaisance, Craig P.; Reuter, Karsten The Journal of Chemical Physics, Vol. 147, Issue 15 https://doi.org/10.1063/1.4989511	journal	October 2017
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Physical time scale in kinetic Monte Carlo simulations of continuous-time Markov chains Serebrinsky, Santiago A. Physical Review E, Vol. 83, Issue 3 https://doi.org/10.1103/PhysRevE.83.037701	journal	March 2011
The Steady State of Heterogeneous Catalysis, Studied by First-Principles Statistical Mechanics Reuter, Karsten; Frenkel, Daan; Scheffler, Matthias Physical Review Letters, Vol. 93, Issue 11 https://doi.org/10.1103/PhysRevLett.93.116105	journal	September 2004
Single-Molecule Enzymatic Dynamics Lu, H. P. Science, Vol. 282, Issue 5395 https://doi.org/10.1126/science.282.5395.1877	journal	December 1998
Relativistic compact effective potentials and efficient, shared-exponent basis sets for the third-, fourth-, and fifth-row atoms Stevens, Walter J.; Krauss, Morris; Basch, Harold Canadian Journal of Chemistry, Vol. 70, Issue 2 https://doi.org/10.1139/v92-085	journal	February 1992
A Practical Guide to Surface Kinetic Monte Carlo Simulations Andersen, Mie; Panosetti, Chiara; Reuter, Karsten Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00202	journal	April 2019

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Computational Investigation of the Role of Active Site Heterogeneity for aSupported Organovanadium(III) Hydrogenation Catalyst

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