Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression

Abstract

Ab initio computational studies have made tremendous progress in describing the behavior of molecular (homogeneous) catalysts and crystalline versions of heterogeneous catalysts, but not for amorphous heterogeneous catalysts. Even widely used industrial amorphous catalysts like atomically dispersed Cr on silica remain poorly understood and largely intractable to computational investigation. The central problems are that (i) the amorphous support presents an unknown quenched disordered structure, (ii) metal atoms attach to various surface grafting sites with different rates, and (iii) the resulting grafted sites have different activation and catalytic reaction kinetics. This study combines kernel regression and importance sampling techniques to efficiently model grafting of metal ions onto a non-uniform ensemble of support environments. Our analysis uses a simple model of the quenched disordered support environment, grafting chemistry, and catalytic activity of the resulting grafted sites.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3]
+ Show Author Affiliations
  1. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering
  2. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering. Dept. of Chemistry & Biochemistry
  3. Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemical & Biomolecular Engineering. Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States); Univ. of Kansas, Lawrence, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1800093
Alternate Identifier(s):
OSTI ID: 1575096
Grant/Contract Number:  
FG02-03ER15467; SC0019488; 1725797; 1605867
Resource Type:
Accepted Manuscript
Journal Name:
Reaction Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2058-9883
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Khan, Salman A., Vandervelden, Craig A., Scott, Susannah L., and Peters, Baron. Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression. United States: N. p., 2019. Web. doi:10.1039/c9re00357f.
Copy to clipboard
Khan, Salman A., Vandervelden, Craig A., Scott, Susannah L., & Peters, Baron. Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression. United States. https://doi.org/10.1039/c9re00357f
Copy to clipboard
Khan, Salman A., Vandervelden, Craig A., Scott, Susannah L., and Peters, Baron. Thu . "Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression". United States. https://doi.org/10.1039/c9re00357f. https://www.osti.gov/servlets/purl/1800093.
Copy to clipboard
@article{osti_1800093,
title = {Grafting metal complexes onto amorphous supports: from elementary steps to catalyst site populations via kernel regression},
author = {Khan, Salman A. and Vandervelden, Craig A. and Scott, Susannah L. and Peters, Baron},
abstractNote = {Ab initio computational studies have made tremendous progress in describing the behavior of molecular (homogeneous) catalysts and crystalline versions of heterogeneous catalysts, but not for amorphous heterogeneous catalysts. Even widely used industrial amorphous catalysts like atomically dispersed Cr on silica remain poorly understood and largely intractable to computational investigation. The central problems are that (i) the amorphous support presents an unknown quenched disordered structure, (ii) metal atoms attach to various surface grafting sites with different rates, and (iii) the resulting grafted sites have different activation and catalytic reaction kinetics. This study combines kernel regression and importance sampling techniques to efficiently model grafting of metal ions onto a non-uniform ensemble of support environments. Our analysis uses a simple model of the quenched disordered support environment, grafting chemistry, and catalytic activity of the resulting grafted sites.},
doi = {10.1039/c9re00357f},
journal = {Reaction Chemistry & Engineering},
number = 1,
volume = 5,
place = {United States},
year = {Thu Oct 31 00:00:00 EDT 2019},
month = {Thu Oct 31 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/c9re00357f
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Oxidative dehydrogenation of propane using lattice oxygen of vanadium oxides on silica
journal, January 2011

  • Fukudome, Kenta; Ikenaga, Na-oki; Miyake, Takanori
  • Catalysis Science & Technology, Vol. 1, Issue 6
  • DOI: 10.1039/c1cy00115a

Molecular-Level Insight into Cr/Silica Phillips-Type Catalysts: Polymerization-Active Dinuclear Chromium Sites
journal, March 2002

Structure of Isolated Molybdenum(VI) and Molybdenum(IV) Oxide Species on Silica: Periodic and Cluster DFT Studies
journal, February 2012

  • Handzlik, Jarosław; Ogonowski, Jan
  • The Journal of Physical Chemistry C, Vol. 116, Issue 9
  • DOI: 10.1021/jp207385h

Application of the ONIOM (QM/QM) method in the study of molybdena–silica system active in olefin metathesis
journal, January 2007

  • Handzlik, Jarosław
  • International Journal of Quantum Chemistry, Vol. 107, Issue 11
  • DOI: 10.1002/qua.21397

Catalytic sites in silica-supported titanium catalysts: silsesquioxane complexes as models
journal, July 2005

Reexamining the evidence for proton transfers in ethylene polymerization
journal, July 2015

  • Peters, Baron; Scott, Susannah L.; Fong, Anthony
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 31
  • DOI: 10.1073/pnas.1422589112

Reassessment of the Electronic Structure of Cr(VI) Sites Supported on Amorphous Silica and Implications for Cr Coordination Number
journal, February 2018

  • Peek, Nathan M.; Jeffcoat, David B.; Moisii, Cristina
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b12079

Mono- and Dinuclear Silica-Supported Titanium(IV) Complexes and the Effect of TiOTi Connectivity on Reactivity
journal, August 1999

  • Bouh, Abdillahi Omar; Rice, Gordon L.; Scott, Susannah L.
  • Journal of the American Chemical Society, Vol. 121, Issue 31
  • DOI: 10.1021/ja9829160

How Enzymes Work: Analysis by Modern Rate Theory and Computer Simulations
journal, January 2004

Common Features of Extraordinary Rate Theories
journal, May 2015

Catalysis by Doped Oxides
journal, December 2012

  • McFarland, Eric W.; Metiu, Horia
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300418s

Accurate Amorphous Silica Surface Models from First-Principles Thermodynamics of Surface Dehydroxylation
journal, April 2014

  • Ewing, Christopher S.; Bhavsar, Saurabh; Veser, Götz
  • Langmuir, Vol. 30, Issue 18
  • DOI: 10.1021/la500422p

Oxygen-Coverage Effects on Molecular Dissociations at a Pt Metal Surface
journal, February 2009

Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design
journal, June 2016

Single atom catalysts on amorphous supports: A quenched disorder perspective
journal, March 2015

  • Peters, Baron; Scott, Susannah L.
  • The Journal of Chemical Physics, Vol. 142, Issue 10
  • DOI: 10.1063/1.4914145

Theoretical Study of the Mechanism of Surface Methoxy and Dimethyl Ether Formation from Methanol Catalyzed by Zeolitic Protons
journal, March 1997

  • Blaszkowski, Solange R.; van Santen, Rutger A.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 13
  • DOI: 10.1021/jp962006+

Hydrogenation of CO on a silica surface: An embedded cluster approach
journal, April 2008

  • Goumans, T. P. M.; Catlow, C. Richard A.; Brown, Wendy A.
  • The Journal of Chemical Physics, Vol. 128, Issue 13
  • DOI: 10.1063/1.2888933

Computational Support for Phillips Catalyst Initiation via Cr–C Bond Homolysis in a Chromacyclopentane Site
journal, January 2018

Evidence for the Pairwise Disposition of Grafting Sites on Highly Dehydroxylated Silicas via Their Reactions with Ga(CH 3 ) 3
journal, April 2011

  • Fleischman, Samuel D.; Scott, Susannah L.
  • Journal of the American Chemical Society, Vol. 133, Issue 13
  • DOI: 10.1021/ja108905p

An X-ray Absorption Study of Two VOCl 3 -Modified Silicas:  Evidence for Chloride−Silica Interactions
journal, March 2005

  • Deguns, Eric W.; Taha, Ziyad; Meitzner, George D.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 11
  • DOI: 10.1021/jp045886y

VO x /SiO 2 Catalyst Prepared by Grafting VOCl 3 on Silica for Oxidative Dehydrogenation of Propane
journal, September 2015

Chromium Oxide Species Supported on Silica: A Representative Periodic DFT Model
journal, December 2011

  • Guesmi, Hazar; Tielens, Frederik
  • The Journal of Physical Chemistry C, Vol. 116, Issue 1
  • DOI: 10.1021/jp209680r

The Mechanism of Cellulose Hydrolysis by a Two-Step, Retaining Cellobiohydrolase Elucidated by Structural and Transition Path Sampling Studies
journal, December 2013

  • Knott, Brandon C.; Haddad Momeni, Majid; Crowley, Michael F.
  • Journal of the American Chemical Society, Vol. 136, Issue 1
  • DOI: 10.1021/ja410291u

Parameters for the Description of Transition States
journal, March 1953

Ab Initio Study of the Hydroxylated Surface of Amorphous Silica: A Representative Model
journal, May 2008

  • Tielens, Frederik; Gervais, Christel; Lambert, Jean François
  • Chemistry of Materials, Vol. 20, Issue 10
  • DOI: 10.1021/cm8001173

Computational insights into reduction of the Phillips CrOx/SiO2 catalyst by ethylene and CO
journal, March 2018

The ONIOM Method and Its Applications
journal, April 2015

  • Chung, Lung Wa; Sameera, W. M. C.; Ramozzi, Romain
  • Chemical Reviews, Vol. 115, Issue 12
  • DOI: 10.1021/cr5004419

Nature of WO x Sites on SiO 2 and Their Molecular Structure–Reactivity/Selectivity Relationships for Propylene Metathesis
journal, April 2016

Analysis of silica-supported vanadia by X-ray absorption spectroscopy: Combined theoretical and experimental studies
journal, March 2009

Properties and structure of vitreous silica. II
journal, January 1971

Semiconductors Used in Photovoltaic and Photocatalytic Devices: Assessing Fundamental Properties from DFT
journal, March 2014

  • Le Bahers, Tangui; Rérat, Michel; Sautet, Philippe
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp409724c

Analysis of the Reaction Mechanism and Catalytic Activity of Metal-Substituted Beta Zeolite for the Isomerization of Glucose to Fructose
journal, April 2014

  • Li, Yi-Pei; Head-Gordon, Martin; Bell, Alexis T.
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs401054f

Role of metal oxide support in redox reactions of iron oxide for chemical looping applications: experiments and density functional theory calculations
journal, January 2011

  • Li, Fanxing; Luo, Siwei; Sun, Zhenchao
  • Energy & Environmental Science, Vol. 4, Issue 9, p. 3661-3667
  • DOI: 10.1039/c1ee01325d

The Importance of Ensemble Averaging in Enzyme Kinetics
journal, December 2014

  • Masgrau, Laura; Truhlar, Donald G.
  • Accounts of Chemical Research, Vol. 48, Issue 2
  • DOI: 10.1021/ar500319e

Rate-Enhancing Roles of Water Molecules in Methyltrioxorhenium-Catalyzed Olefin Epoxidation by Hydrogen Peroxide
journal, July 2015

  • Goldsmith, Bryan R.; Hwang, Taeho; Seritan, Stefan
  • Journal of the American Chemical Society, Vol. 137, Issue 30
  • DOI: 10.1021/jacs.5b03750

Strain effect and dual initiation pathway in CrIII/SiO2 polymerization catalysts from amorphous periodic models
journal, February 2017

Properties and structure of vitreous silica. I
journal, November 1970

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR
journal, March 2017

  • Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 11
  • DOI: 10.1021/acs.jpcc.7b01658

Origin of the Raman bands, D1 and D2, in high surface area and vitreous silicas
journal, January 1992

The surface structure of silica gel
journal, August 1968

  • Peri, J. B.; Hensley, A. L.
  • The Journal of Physical Chemistry, Vol. 72, Issue 8
  • DOI: 10.1021/j100854a041

Proton transfers are key elementary steps in ethylene polymerization on isolated chromium(III) silicates
journal, July 2014

  • Delley, M. F.; Nunez-Zarur, F.; Conley, M. P.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 32
  • DOI: 10.1073/pnas.1405314111

Isolated catalyst sites on amorphous supports: A systematic algorithm for understanding heterogeneities in structure and reactivity
journal, May 2013

  • Goldsmith, Bryan R.; Sanderson, Evan D.; Bean, Daniel
  • The Journal of Chemical Physics, Vol. 138, Issue 20
  • DOI: 10.1063/1.4807384

Simulations of Ammonia Adsorption for the Characterization of Acid Sites in Metal-Doped Amorphous Silicates
journal, September 2017

  • Jystad, Amy M.; Biancardi, Alessandro; Caricato, Marco
  • The Journal of Physical Chemistry C, Vol. 121, Issue 40
  • DOI: 10.1021/acs.jpcc.7b08113

Liquid-Phase Modeling in Heterogeneous Catalysis
journal, January 2018

A Density Functional Theory Study of the Oxidation of Methanol to Formaldehyde over Vanadia Supported on Silica, Titania, and Zirconia
journal, August 2002

  • Khaliullin, Rustam Z.; Bell, Alexis T.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 32
  • DOI: 10.1021/jp014695h

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments
journal, December 2012

  • Rimola, Albert; Costa, Dominique; Sodupe, Mariona
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr3003054

Propylene epoxidation over titanium-on-silica catalyst—the heart of the SMPO process
journal, September 2004

Preparation and in-Situ Spectroscopic Characterization of Molecularly Dispersed Titanium Oxide on Silica
journal, July 1998

  • Gao, Xingtao; Bare, Simon R.; Fierro, J. L. G.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 29
  • DOI: 10.1021/jp981423e

The surface chemistry of amorphous silica. Zhuravlev model
journal, November 2000

Raman investigation of ring configurations in vitreous silica
journal, July 1981

  • Sharma, Shiv K.; Mammone, Joseph F.; Nicol, Malcolm F.
  • Nature, Vol. 292, Issue 5819
  • DOI: 10.1038/292140a0

Spectroscopic and structural characterization of Cr(II)/SiO2 active site precursors in model Phillips polymerization catalysts
journal, September 2012

Site-averaged kinetics for catalysts on amorphous supports: an importance learning algorithm
journal, January 2019

  • Vandervelden, Craig; Khan, Salman Ahmad; Scott, Susannah L.
  • Reaction Chemistry & Engineering
  • DOI: 10.1039/C9RE00356H

The surprising oxidation state of fumed silica and the nature of water binding to silicon oxides and hydroxides
journal, January 2011

Surface structure and chemistry of high surface area silica gels
journal, April 1990

Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities
journal, January 2016

Role of Environment for Catalysis of the DNA Repair Enzyme MutY
journal, May 2012

  • Brunk, Elizabeth; Arey, J. Samuel; Rothlisberger, Ursula
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja301714j

Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas
journal, January 2016

  • Oschatz, M.; van Deelen, T. W.; Weber, J. L.
  • Catalysis Science & Technology, Vol. 6, Issue 24
  • DOI: 10.1039/C6CY01251E

A review of multiscale modeling of metal-catalyzed reactions: Mechanism development for complexity and emergent behavior
journal, October 2011

  • Salciccioli, M.; Stamatakis, M.; Caratzoulas, S.
  • Chemical Engineering Science, Vol. 66, Issue 19
  • DOI: 10.1016/j.ces.2011.05.050

Structure of Monomeric Chromium(VI) Oxide Species Supported on Silica: Periodic and Cluster DFT Studies
journal, April 2013

  • Handzlik, Jarosław; Grybos, Robert; Tielens, Frederik
  • The Journal of Physical Chemistry C, Vol. 117, Issue 16
  • DOI: 10.1021/jp3103035

Molecular dynamics as a tool to study heterogeneity in zeolites – Effect of Na+ cations on diffusion of CO2 and N2 in Na-ZSM-5
journal, January 2015

Formation of Digallium Sites in the Reaction of Trimethylgallium with Silica
journal, April 2006

  • Taha, Ziyad A.; Deguns, Eric W.; Chattopadhyay, Swarup
  • Organometallics, Vol. 25, Issue 8
  • DOI: 10.1021/om051034o

Kernel methods in machine learning
journal, June 2008

  • Hofmann, Thomas; Schölkopf, Bernhard; Smola, Alexander J.
  • The Annals of Statistics, Vol. 36, Issue 3
  • DOI: 10.1214/009053607000000677

Silica-Supported, Single-Site Titanium Catalysts for Olefin Epoxidation. A Molecular Precursor Strategy for Control of Catalyst Structure
journal, July 2002

  • Jarupatrakorn, Jonggol; Tilley, T. Don
  • Journal of the American Chemical Society, Vol. 124, Issue 28
  • DOI: 10.1021/ja0202208

Computational Kinetic Discrimination of Ethylene Polymerization Mechanisms for the Phillips (Cr/SiO 2 ) Catalyst
journal, May 2015

Impact of Support Interactions for Single-Atom Molybdenum Catalysts on Amorphous Silica
journal, November 2016

  • Ewing, Christopher S.; Bagusetty, Abhishek; Patriarca, Evan G.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 48
  • DOI: 10.1021/acs.iecr.6b03558

Reactions of HMDS, TiCl 4 , ZrCl 4 , and AlCl 3 with Silica As Interpreted from Low-Frequency Diffuse Reflectance Infrared Spectra
journal, December 1997

  • Kytökivi, Arla; Haukka, Suvi
  • The Journal of Physical Chemistry B, Vol. 101, Issue 49
  • DOI: 10.1021/jp971822u

Surface organometallic chemistry in heterogeneous catalysis
journal, January 2018

  • Samantaray, Manoja K.; Pump, Eva; Bendjeriou-Sedjerari, Anissa
  • Chemical Society Reviews, Vol. 47, Issue 22
  • DOI: 10.1039/C8CS00356D

Kernel methods in machine learning
text, January 2007

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: