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

García, Andres; Slowing, Igor I.; Evans, James W.

doi:10.1063/1.5037618

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

Journal Article · Mon Jul 09 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5037618· OSTI ID:1464469

García, Andres ^[1];

^[2];

^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States). Division of Chemical and Biological Sciences, and Dept. of Physics and Astronomy
Ames Lab. and Iowa State Univ., Ames, IA (United States). Division of Chemical and Biological Sciences, and Dept. of of Chemistry

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.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1464469

Alternate ID(s):: OSTI ID: 1459478

Report Number(s):: IS-J-9645

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 2; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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References (51)

Hydrodynamic properties of macromolecular complexes. I. Translation De La Torre, Jose Garcia; Bloomfield, Victor A. Biopolymers, Vol. 16, Issue 8 https://doi.org/10.1002/bip.1977.360160811	journal	August 1977
Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts Jiao, Feng; Frei, Heinz Angewandte Chemie International Edition, Vol. 48, Issue 10 https://doi.org/10.1002/anie.200805534	journal	February 2009
Molecular Dynamics Simulations of Water Structure and Diffusion in Silica Nanopores Bourg, Ian C.; Steefel, Carl I. The Journal of Physical Chemistry C, Vol. 116, Issue 21 https://doi.org/10.1021/jp301299a	journal	May 2012
Diffusion and reaction in high-occupancy zeolite catalysts—I. A stochastic theory Tsikoyiannis, John G.; Wei, James Chemical Engineering Science, Vol. 46, Issue 1 https://doi.org/10.1016/0009-2509(91)80132-i	journal	January 1991
Observation of Fractional Stokes-Einstein Behavior in the Simplest Hydrogen-Bonded Liquid Fernandez-Alonso, F.; Bermejo, F. J.; McLain, S. E. Physical Review Letters, Vol. 98, Issue 7 https://doi.org/10.1103/physrevlett.98.077801	journal	February 2007
Mouvement Brownien d'un ellipsoide (II). Rotation libre et dépolarisation des fluorescences. Translation et diffusion de molécules ellipsoidales Perrin, Francis Journal de Physique et le Radium, Vol. 7, Issue 1 https://doi.org/10.1051/jphysrad:01936007010100	journal	January 1936
Neutron Scattering Study on Dynamics of Water Molecules in MCM-41 Takahara, Shuichi; Nakano, Masatsugu; Kittaka, Shigeharu The Journal of Physical Chemistry B, Vol. 103, Issue 28 https://doi.org/10.1021/jp984136j	journal	July 1999
Silanol-Assisted Carbinolamine Formation in an Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation by Fragmentation Methods de Lima Batista, Ana P.; Zahariev, Federico; Slowing, Igor I. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b08446	journal	November 2015
Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica Maschmeyer, Thomas; Rey, Fernando; Sankar, Gopinathan Nature, Vol. 378, Issue 6553 https://doi.org/10.1038/378159a0	journal	November 1995
Diffusion with “collisions” between particles Harris, T. E. Journal of Applied Probability, Vol. 2, Issue 02 https://doi.org/10.1017/s002190020010868x	journal	December 1965
Neopentane Conversion Catalyzed by Pd in L-Zeolite: Effects of Protons, Ions, and Zeolite Structure Karpinski, Z.; Gandhi, S. N.; Sachtler, W. M. H. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1144	journal	June 1993
T RANSITION P ATH S AMPLING : Throwing Ropes Over Rough Mountain Passes, in the Dark Bolhuis, Peter G.; Chandler, David; Dellago, Christoph Annual Review of Physical Chemistry, Vol. 53, Issue 1 https://doi.org/10.1146/annurev.physchem.53.082301.113146	journal	October 2002
A Guide to First-Passage Processes Redner, Sidney https://doi.org/10.1017/CBO9780511606014	book	January 2001
A new family of mesoporous molecular sieves prepared with liquid crystal templates Beck, J. S.; Vartuli, J. C.; Roth, W. J. Journal of the American Chemical Society, Vol. 114, Issue 27, p. 10834-10843 https://doi.org/10.1021/ja00053a020	journal	December 1992
Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts Kandel, Kapil; Althaus, Stacey M.; Peeraphatdit, Chorthip Journal of Catalysis, Vol. 291 https://doi.org/10.1016/j.jcat.2012.04.005	journal	July 2012
Brownian Motion of Arbitrarily Shaped Particles in Two Dimensions Chakrabarty, Ayan; Konya, Andrew; Wang, Feng Langmuir, Vol. 30, Issue 46 https://doi.org/10.1021/la5037053	journal	November 2014
Molecular Dynamics Simulations of Aldol Condensation Catalyzed by Alkylamine-Functionalized Crystalline Silica Surfaces Kim, Ki Chul; Moschetta, Eric G.; Jones, Christopher W. Journal of the American Chemical Society, Vol. 138, Issue 24 https://doi.org/10.1021/jacs.6b03309	journal	June 2016
An Efficient Computational Method for Predicting Rotational Diffusion Tensors of Globular Proteins Using an Ellipsoid Representation Ryabov, Yaroslav E.; Geraghty, Charles; Varshney, Amitabh Journal of the American Chemical Society, Vol. 128, Issue 48 https://doi.org/10.1021/ja062715t	journal	December 2006
Transportation of Aqueous and Alcoholic Solutions through the Nanochannel of MCM-41: A Spin Probe Electron Spin Resonance Study Okazaki, Masaharu; Jin, Ping; Ohta, Kazutoku The Journal of Physical Chemistry C, Vol. 113, Issue 25 https://doi.org/10.1021/jp901908z	journal	May 2009
Normal, single-file, and dual-mode diffusion of binary adsorbate mixtures in AlPO4-5 Sholl, David S.; Fichthorn, Kristen A. The Journal of Chemical Physics, Vol. 107, Issue 11 https://doi.org/10.1063/1.474779	journal	September 1997
Brownian Motion of Boomerang Colloidal Particles Chakrabarty, Ayan; Konya, Andrew; Wang, Feng Physical Review Letters, Vol. 111, Issue 16 https://doi.org/10.1103/physrevlett.111.160603	journal	October 2013
Freezing and Melting of Water Confined in Silica Nanopores Findenegg, Gerhard H.; Jähnert, Susanne; Akcakayiran, Dilek ChemPhysChem, Vol. 9, Issue 18 https://doi.org/10.1002/cphc.200800616	journal	November 2008
Mesoporous Silica Nanoparticles for Intracellular Delivery of Membrane-Impermeable Proteins Slowing, Igor I.; Trewyn, Brian G.; Lin, Victor S. -Y. Journal of the American Chemical Society, Vol. 129, Issue 28 https://doi.org/10.1021/ja0719780	journal	July 2007
Mouvement brownien d'un ellipsoide - I. Dispersion diélectrique pour des molécules ellipsoidales Perrin, Francis Journal de Physique et le Radium, Vol. 5, Issue 10 https://doi.org/10.1051/jphysrad:01934005010049700	journal	January 1934
An elementary singularity-free Rotational Brownian Dynamics algorithm for anisotropic particles Ilie, Ioana M.; Briels, Wim J.; den Otter, Wouter K. The Journal of Chemical Physics, Vol. 142, Issue 11 https://doi.org/10.1063/1.4914322	journal	March 2015
Tuning Cooperativity by Controlling the Linker Length of Silica-Supported Amines in Catalysis and CO ₂ Capture Brunelli, Nicholas A.; Didas, Stephanie A.; Venkatasubbaiah, Krishnan Journal of the American Chemical Society, Vol. 134, Issue 34 https://doi.org/10.1021/ja305601g	journal	August 2012
Translation-rotation decoupling of colloidal clusters of various symmetries Anthony, Stephen M.; Kim, Minsu; Granick, Steve The Journal of Chemical Physics, Vol. 129, Issue 24 https://doi.org/10.1063/1.3043443	journal	December 2008
Tuning Single-Molecule Dynamics in Functionalized Mesoporous Silica Lebold, Timo; Mühlstein, Lea A.; Blechinger, Julia Chemistry - A European Journal, Vol. 15, Issue 7 https://doi.org/10.1002/chem.200801380	journal	February 2009
Steady-state properties of single-file systems with conversion Nedea, S. V.; Jansen, A. P. J.; Lukkien, J. J. Physical Review E, Vol. 65, Issue 6 https://doi.org/10.1103/physreve.65.066701	journal	June 2002
Interplay between Anomalous Transport and Catalytic Reaction Kinetics in Single-File Nanoporous Systems Liu, Da-Jiang; Wang, Jing; Ackerman, David M. ACS Catalysis, Vol. 1, Issue 7 https://doi.org/10.1021/cs200115c	journal	May 2011
Tracer Exchange and Catalytic Reaction in Single-File Systems Rodenbeck, C.; Karger, J.; Hahn, K. Journal of Catalysis, Vol. 157, Issue 2 https://doi.org/10.1006/jcat.1995.1331	journal	December 1995
A consistent correlation approach to single file diffusion with reaction Okino, Miles S.; Snurr, Randall Q.; Kung, Harold H. The Journal of Chemical Physics, Vol. 111, Issue 5 https://doi.org/10.1063/1.479493	journal	August 1999
Cooperative Catalysis with Acid–Base Bifunctional Mesoporous Silica: Impact of Grafting and Co-condensation Synthesis Methods on Material Structure and Catalytic Properties Brunelli, Nicholas A.; Venkatasubbaiah, Krishnan; Jones, Christopher W. Chemistry of Materials, Vol. 24, Issue 13 https://doi.org/10.1021/cm300753z	journal	June 2012
Langevin and Fokker-Planck Analyses of Inhibited Molecular Passing Processes Controlling Transport and Reactivity in Nanoporous Materials Wang, Chi-Jen; Ackerman, David M.; Slowing, Igor I. Physical Review Letters, Vol. 113, Issue 3 https://doi.org/10.1103/physrevlett.113.038301	journal	July 2014
Boundary Conditions for Diffusion-Mediated Processes within Linear Nanopores: Exact Treatment of Coupling to an Equilibrated External Fluid García, Andrés; Evans, James W. The Journal of Physical Chemistry C, Vol. 121, Issue 16 https://doi.org/10.1021/acs.jpcc.7b01273	journal	April 2017
Effects of amine structure and base strength on acid–base cooperative aldol condensation Lauwaert, Jeroen; De Canck, Els; Esquivel, Dolores Catalysis Today, Vol. 246 https://doi.org/10.1016/j.cattod.2014.08.007	journal	May 2015
Stokes–Einstein–Debye Failure in Molecular Orientational Diffusion: Exception or Rule? Turton, David A.; Wynne, Klaas The Journal of Physical Chemistry B, Vol. 118, Issue 17 https://doi.org/10.1021/jp5012457	journal	April 2014
Kinetic Monte Carlo Simulation of Statistical Mechanical Models and Coarse-Grained Mesoscale Descriptions of Catalytic Reaction–Diffusion Processes: 1D Nanoporous and 2D Surface Systems Liu, Da-Jiang; Garcia, Andres; Wang, Jing Chemical Reviews, Vol. 115, Issue 12 https://doi.org/10.1021/cr500453t	journal	April 2015
Brownian dynamics of confined rigid bodies Delong, Steven; Balboa Usabiaga, Florencio; Donev, Aleksandar The Journal of Chemical Physics, Vol. 143, Issue 14 https://doi.org/10.1063/1.4932062	journal	October 2015
Characterizing adsorbate passage in molecular sieve pores Sholl, David S. Chemical Engineering Journal, Vol. 74, Issue 1-2 https://doi.org/10.1016/s1385-8947(99)00050-9	journal	July 1999
Cooperative Catalysis by General Acid and Base Bifunctionalized Mesoporous Silica Nanospheres Huh, Seong; Chen, Hung-Ting; Wiench, Jerzy W. Angewandte Chemie International Edition, Vol. 44, Issue 12 https://doi.org/10.1002/anie.200462424	journal	March 2005
Variational Treatment of Hydrodynamic Interaction in Polymers Rotne, Jens; Prager, Stephen The Journal of Chemical Physics, Vol. 50, Issue 11 https://doi.org/10.1063/1.1670977	journal	June 1969
Kinetic and Mechanistic Examination of Acid–Base Bifunctional Aminosilica Catalysts in Aldol and Nitroaldol Condensations Collier, Virginia E.; Ellebracht, Nathan C.; Lindy, George I. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b02398	journal	December 2015
Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling Wang, Jing; Ackerman, David M.; Lin, Victor S. -Y. The Journal of Chemical Physics, Vol. 138, Issue 13 https://doi.org/10.1063/1.4798463	journal	April 2013
A general ellipsoid cannot always serve as a model for the rotational diffusion properties of arbitrarily shaped rigid molecules Wegener, W. A.; Koester, V. J.; Dowben, R. M. Proceedings of the National Academy of Sciences, Vol. 76, Issue 12 https://doi.org/10.1073/pnas.76.12.6356	journal	December 1979
Cooperative Catalysis by General Acid and Base Bifunctionalized Mesoporous Silica Nanospheres Huh, Seong; Chen, Hung-Ting; Wiench, Jerzy W. Angewandte Chemie, Vol. 117, Issue 12 https://doi.org/10.1002/ange.200462424	journal	March 2005
A Guide to First-passage Processes Stoyanov, Jordan Journal of the Royal Statistical Society: Series D (The Statistician), Vol. 52, Issue 2 https://doi.org/10.1111/1467-9884.t01-7-00356	journal	July 2003
The Langevin Equation: With Applications to Stochastic Problems in Physics, Chemistry and Electrical Engineering Coffey, William T.; Kalmykov, Yuri P. World Scientific Series in Contemporary Chemical Physics, Vol. 28 https://doi.org/10.1142/10490	book	May 2017
Diffusion with “collisions” between particles Harris, T. E. Journal of Applied Probability, Vol. 2, Issue 2 https://doi.org/10.2307/3212197	journal	December 1965
Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts Jiao, Feng; Frei, Heinz Angewandte Chemie, Vol. 121, Issue 10 https://doi.org/10.1002/ange.200805534	journal	February 2009
Steady-State Properties of Single-File Systems with Conversion Nedea, S. V.; Jansen, A. P. J.; Lukkien, J. J. arXiv https://doi.org/10.48550/arxiv.physics/0201070	text	January 2002

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