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Title: Pore diameter dependence of catalytic activity: p-nitrobenzaldehyde conversion to an aldol product in amine-functionalized mesoporous silica

Abstract

The reaction yield for conversion of p-nitrobenzaldehyde (PNB) to an aldol product in amine-functionalized mesoporous silica nanoparticles (MSN) exhibits a 20-fold enhancement for a modest increase in pore diameter, d. This enhanced catalytic activity is shown to reflect a strong increase in the “passing propensity,” P, of reactant and product species inside the pores. We find that P ≈ 0, corresponding to single-file diffusion, applies for the smallest d which still significantly exceeds the linear dimensions of PNB and the aldol product. However, in this regime of narrow pores, these elongated species must align with each other and with the pore axis in order to pass. Thus, P reflects both translational and rotational diffusion. Langevin simulation accounting for these features is used to determine P versus d. The results are also augmented by analytic theory for small and large d where simulation is inefficient. The connection with the catalytic activity and yield is achieved by the incorporation of results for P into a multi-scale modeling framework. Specifically, we apply a spatially coarse-grained (CG) stochastic model for the overall catalytic reaction-diffusion process in MSN. Pores are treated as linear arrays of cells from the ends of which species adsorb and desorb,more » and between which species hop and exchange, with the exchange rate reflecting P. CG model predictions including yield are assessed by Kinetic Monte Carlo simulation.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Division of Chemical and Biological Sciences, and Dept. of Physics and Astronomy
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States). Division of Chemical and Biological Sciences, and Dept. of of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1464469
Alternate Identifier(s):
OSTI ID: 1459478
Report Number(s):
IS-J-9645
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

García, Andres, Slowing, Igor I., and Evans, James W. Pore diameter dependence of catalytic activity: p-nitrobenzaldehyde conversion to an aldol product in amine-functionalized mesoporous silica. United States: N. p., 2018. Web. doi:10.1063/1.5037618.
García, Andres, Slowing, Igor I., & Evans, James W. Pore diameter dependence of catalytic activity: p-nitrobenzaldehyde conversion to an aldol product in amine-functionalized mesoporous silica. United States. doi:10.1063/1.5037618.
García, Andres, Slowing, Igor I., and Evans, James W. Mon . "Pore diameter dependence of catalytic activity: p-nitrobenzaldehyde conversion to an aldol product in amine-functionalized mesoporous silica". United States. doi:10.1063/1.5037618. https://www.osti.gov/servlets/purl/1464469.
@article{osti_1464469,
title = {Pore diameter dependence of catalytic activity: p-nitrobenzaldehyde conversion to an aldol product in amine-functionalized mesoporous silica},
author = {García, Andres and Slowing, Igor I. and Evans, James W.},
abstractNote = {The reaction yield for conversion of p-nitrobenzaldehyde (PNB) to an aldol product in amine-functionalized mesoporous silica nanoparticles (MSN) exhibits a 20-fold enhancement for a modest increase in pore diameter, d. This enhanced catalytic activity is shown to reflect a strong increase in the “passing propensity,” P, of reactant and product species inside the pores. We find that P ≈ 0, corresponding to single-file diffusion, applies for the smallest d which still significantly exceeds the linear dimensions of PNB and the aldol product. However, in this regime of narrow pores, these elongated species must align with each other and with the pore axis in order to pass. Thus, P reflects both translational and rotational diffusion. Langevin simulation accounting for these features is used to determine P versus d. The results are also augmented by analytic theory for small and large d where simulation is inefficient. The connection with the catalytic activity and yield is achieved by the incorporation of results for P into a multi-scale modeling framework. Specifically, we apply a spatially coarse-grained (CG) stochastic model for the overall catalytic reaction-diffusion process in MSN. Pores are treated as linear arrays of cells from the ends of which species adsorb and desorb, and between which species hop and exchange, with the exchange rate reflecting P. CG model predictions including yield are assessed by Kinetic Monte Carlo simulation.},
doi = {10.1063/1.5037618},
journal = {Journal of Chemical Physics},
number = 2,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

Hydrodynamic properties of macromolecular complexes. I. Translation
journal, August 1977


Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts
journal, February 2009

  • Jiao, Feng; Frei, Heinz
  • Angewandte Chemie International Edition, Vol. 48, Issue 10
  • DOI: 10.1002/anie.200805534

Molecular Dynamics Simulations of Water Structure and Diffusion in Silica Nanopores
journal, May 2012

  • Bourg, Ian C.; Steefel, Carl I.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 21
  • DOI: 10.1021/jp301299a

Diffusion and reaction in high-occupancy zeolite catalysts—I. A stochastic theory
journal, January 1991


Observation of Fractional Stokes-Einstein Behavior in the Simplest Hydrogen-Bonded Liquid
journal, February 2007


Neutron Scattering Study on Dynamics of Water Molecules in MCM-41
journal, July 1999

  • Takahara, Shuichi; Nakano, Masatsugu; Kittaka, Shigeharu
  • The Journal of Physical Chemistry B, Vol. 103, Issue 28
  • DOI: 10.1021/jp984136j

Silanol-Assisted Carbinolamine Formation in an Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation by Fragmentation Methods
journal, November 2015

  • de Lima Batista, Ana P.; Zahariev, Federico; Slowing, Igor I.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b08446

Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica
journal, November 1995

  • Maschmeyer, Thomas; Rey, Fernando; Sankar, Gopinathan
  • Nature, Vol. 378, Issue 6553
  • DOI: 10.1038/378159a0

Diffusion with “collisions” between particles
journal, December 1965


Neopentane Conversion Catalyzed by Pd in L-Zeolite: Effects of Protons, Ions, and Zeolite Structure
journal, June 1993

  • Karpinski, Z.; Gandhi, S. N.; Sachtler, W. M. H.
  • Journal of Catalysis, Vol. 141, Issue 2
  • DOI: 10.1006/jcat.1993.1144

T RANSITION P ATH S AMPLING : Throwing Ropes Over Rough Mountain Passes, in the Dark
journal, October 2002


A new family of mesoporous molecular sieves prepared with liquid crystal templates
journal, December 1992

  • Beck, J. S.; Vartuli, J. C.; Roth, W. J.
  • Journal of the American Chemical Society, Vol. 114, Issue 27, p. 10834-10843
  • DOI: 10.1021/ja00053a020

Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts
journal, July 2012


Brownian Motion of Arbitrarily Shaped Particles in Two Dimensions
journal, November 2014

  • Chakrabarty, Ayan; Konya, Andrew; Wang, Feng
  • Langmuir, Vol. 30, Issue 46
  • DOI: 10.1021/la5037053

Molecular Dynamics Simulations of Aldol Condensation Catalyzed by Alkylamine-Functionalized Crystalline Silica Surfaces
journal, June 2016

  • Kim, Ki Chul; Moschetta, Eric G.; Jones, Christopher W.
  • Journal of the American Chemical Society, Vol. 138, Issue 24
  • DOI: 10.1021/jacs.6b03309

An Efficient Computational Method for Predicting Rotational Diffusion Tensors of Globular Proteins Using an Ellipsoid Representation
journal, December 2006

  • Ryabov, Yaroslav E.; Geraghty, Charles; Varshney, Amitabh
  • Journal of the American Chemical Society, Vol. 128, Issue 48
  • DOI: 10.1021/ja062715t

Transportation of Aqueous and Alcoholic Solutions through the Nanochannel of MCM-41: A Spin Probe Electron Spin Resonance Study
journal, May 2009

  • Okazaki, Masaharu; Jin, Ping; Ohta, Kazutoku
  • The Journal of Physical Chemistry C, Vol. 113, Issue 25
  • DOI: 10.1021/jp901908z

Normal, single-file, and dual-mode diffusion of binary adsorbate mixtures in AlPO4-5
journal, September 1997

  • Sholl, David S.; Fichthorn, Kristen A.
  • The Journal of Chemical Physics, Vol. 107, Issue 11
  • DOI: 10.1063/1.474779

Brownian Motion of Boomerang Colloidal Particles
journal, October 2013


Freezing and Melting of Water Confined in Silica Nanopores
journal, November 2008

  • Findenegg, Gerhard H.; Jähnert, Susanne; Akcakayiran, Dilek
  • ChemPhysChem, Vol. 9, Issue 18
  • DOI: 10.1002/cphc.200800616

Mesoporous Silica Nanoparticles for Intracellular Delivery of Membrane-Impermeable Proteins
journal, July 2007

  • Slowing, Igor I.; Trewyn, Brian G.; Lin, Victor S. -Y.
  • Journal of the American Chemical Society, Vol. 129, Issue 28
  • DOI: 10.1021/ja0719780

Mouvement brownien d'un ellipsoide - I. Dispersion diélectrique pour des molécules ellipsoidales
journal, January 1934


An elementary singularity-free Rotational Brownian Dynamics algorithm for anisotropic particles
journal, March 2015

  • Ilie, Ioana M.; Briels, Wim J.; den Otter, Wouter K.
  • The Journal of Chemical Physics, Vol. 142, Issue 11
  • DOI: 10.1063/1.4914322

Tuning Cooperativity by Controlling the Linker Length of Silica-Supported Amines in Catalysis and CO 2 Capture
journal, August 2012

  • Brunelli, Nicholas A.; Didas, Stephanie A.; Venkatasubbaiah, Krishnan
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • DOI: 10.1021/ja305601g

Translation-rotation decoupling of colloidal clusters of various symmetries
journal, December 2008

  • Anthony, Stephen M.; Kim, Minsu; Granick, Steve
  • The Journal of Chemical Physics, Vol. 129, Issue 24
  • DOI: 10.1063/1.3043443

Tuning Single-Molecule Dynamics in Functionalized Mesoporous Silica
journal, February 2009

  • Lebold, Timo; Mühlstein, Lea A.; Blechinger, Julia
  • Chemistry - A European Journal, Vol. 15, Issue 7
  • DOI: 10.1002/chem.200801380

Steady-state properties of single-file systems with conversion
journal, June 2002


Interplay between Anomalous Transport and Catalytic Reaction Kinetics in Single-File Nanoporous Systems
journal, May 2011

  • Liu, Da-Jiang; Wang, Jing; Ackerman, David M.
  • ACS Catalysis, Vol. 1, Issue 7
  • DOI: 10.1021/cs200115c

Tracer Exchange and Catalytic Reaction in Single-File Systems
journal, December 1995


A consistent correlation approach to single file diffusion with reaction
journal, August 1999

  • Okino, Miles S.; Snurr, Randall Q.; Kung, Harold H.
  • The Journal of Chemical Physics, Vol. 111, Issue 5
  • DOI: 10.1063/1.479493

Cooperative Catalysis with Acid–Base Bifunctional Mesoporous Silica: Impact of Grafting and Co-condensation Synthesis Methods on Material Structure and Catalytic Properties
journal, June 2012

  • Brunelli, Nicholas A.; Venkatasubbaiah, Krishnan; Jones, Christopher W.
  • Chemistry of Materials, Vol. 24, Issue 13
  • DOI: 10.1021/cm300753z

Langevin and Fokker-Planck Analyses of Inhibited Molecular Passing Processes Controlling Transport and Reactivity in Nanoporous Materials
journal, July 2014


Boundary Conditions for Diffusion-Mediated Processes within Linear Nanopores: Exact Treatment of Coupling to an Equilibrated External Fluid
journal, April 2017

  • García, Andrés; Evans, James W.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 16
  • DOI: 10.1021/acs.jpcc.7b01273

Effects of amine structure and base strength on acid–base cooperative aldol condensation
journal, May 2015


Stokes–Einstein–Debye Failure in Molecular Orientational Diffusion: Exception or Rule?
journal, April 2014

  • Turton, David A.; Wynne, Klaas
  • The Journal of Physical Chemistry B, Vol. 118, Issue 17
  • DOI: 10.1021/jp5012457

Brownian dynamics of confined rigid bodies
journal, October 2015

  • Delong, Steven; Balboa Usabiaga, Florencio; Donev, Aleksandar
  • The Journal of Chemical Physics, Vol. 143, Issue 14
  • DOI: 10.1063/1.4932062

Characterizing adsorbate passage in molecular sieve pores
journal, July 1999


Cooperative Catalysis by General Acid and Base Bifunctionalized Mesoporous Silica Nanospheres
journal, March 2005

  • Huh, Seong; Chen, Hung-Ting; Wiench, Jerzy W.
  • Angewandte Chemie International Edition, Vol. 44, Issue 12
  • DOI: 10.1002/anie.200462424

Variational Treatment of Hydrodynamic Interaction in Polymers
journal, June 1969

  • Rotne, Jens; Prager, Stephen
  • The Journal of Chemical Physics, Vol. 50, Issue 11
  • DOI: 10.1063/1.1670977

Kinetic and Mechanistic Examination of Acid–Base Bifunctional Aminosilica Catalysts in Aldol and Nitroaldol Condensations
journal, December 2015

  • Collier, Virginia E.; Ellebracht, Nathan C.; Lindy, George I.
  • ACS Catalysis, Vol. 6, Issue 1
  • DOI: 10.1021/acscatal.5b02398

Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling
journal, April 2013

  • Wang, Jing; Ackerman, David M.; Lin, Victor S. -Y.
  • The Journal of Chemical Physics, Vol. 138, Issue 13
  • DOI: 10.1063/1.4798463

A general ellipsoid cannot always serve as a model for the rotational diffusion properties of arbitrarily shaped rigid molecules
journal, December 1979

  • Wegener, W. A.; Koester, V. J.; Dowben, R. M.
  • Proceedings of the National Academy of Sciences, Vol. 76, Issue 12
  • DOI: 10.1073/pnas.76.12.6356