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Title: Effect of nanoscale flows on the surface structure of nanoporous catalysts

Abstract

Here, the surface structure and composition of a multi-component catalyst are critical factors in determining its catalytic performance. The surface composition can depend on the local pressure of the reacting species, leading to the possibility that the flow through a nanoporous catalyst can affect its structure and reactivity. Here, we explore this possibility for oxidation reactions on nanoporous gold, an AgAu bimetallic catalyst. We use microscopy and digital reconstruction to obtain the morphology of a two-dimensional slice of a nanoporous gold sample. Using lattice Boltzmann fluid dynamics simulations along with thermodynamic models based on first-principles total-energy calculations, we show that some sections of this sample have low local O2 partial pressures when exposed to reaction conditions, which leads to a pure Au surface in these regions, instead of the active bimetallic AgAu phase. We also explore the effect of temperature on the surface structure and find that moderate temperatures (≈300–450 K) should result in the highest intrinsic catalytic performance, in apparent agreement with experimental results.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4];  [5];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Univ. of Rome “Roma Tre,” Rome (Italy)
  3. Harvard Univ., Cambridge, MA (United States); Istituto per le Applicazioni del Calcolo - CNR, Rome (Italy)
  4. Harvard Univ., Cambridge, MA (United States); Univ. of Rome "Tor Vergata", Rome (Italy)
  5. Harvard Univ., Cambridge, MA (United States); Center for Nanoscale Systems, Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388894
Alternate Identifier(s):
OSTI ID: 1365429
Grant/Contract Number:  
SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 21; Related Information: IMASC partners with Harvard University (lead); Fritz Haber Institute; Lawrence Berkeley National Laboratory; Lawrence Livermore National Laboratory; University of Kansas; Tufts University; 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; catalysis (heterogeneous); mesostructured materials; materials and chemistry by design; synthesis (novel materials)

Citation Formats

Montemore, Matthew M., Montessori, Andrea, Succi, Sauro, Barroo, Cédric, Falcucci, Giacomo, Bell, David C., and Kaxiras, Efthimios. Effect of nanoscale flows on the surface structure of nanoporous catalysts. United States: N. p., 2017. Web. doi:10.1063/1.4984614.
Montemore, Matthew M., Montessori, Andrea, Succi, Sauro, Barroo, Cédric, Falcucci, Giacomo, Bell, David C., & Kaxiras, Efthimios. Effect of nanoscale flows on the surface structure of nanoporous catalysts. United States. https://doi.org/10.1063/1.4984614
Montemore, Matthew M., Montessori, Andrea, Succi, Sauro, Barroo, Cédric, Falcucci, Giacomo, Bell, David C., and Kaxiras, Efthimios. Thu . "Effect of nanoscale flows on the surface structure of nanoporous catalysts". United States. https://doi.org/10.1063/1.4984614. https://www.osti.gov/servlets/purl/1388894.
@article{osti_1388894,
title = {Effect of nanoscale flows on the surface structure of nanoporous catalysts},
author = {Montemore, Matthew M. and Montessori, Andrea and Succi, Sauro and Barroo, Cédric and Falcucci, Giacomo and Bell, David C. and Kaxiras, Efthimios},
abstractNote = {Here, the surface structure and composition of a multi-component catalyst are critical factors in determining its catalytic performance. The surface composition can depend on the local pressure of the reacting species, leading to the possibility that the flow through a nanoporous catalyst can affect its structure and reactivity. Here, we explore this possibility for oxidation reactions on nanoporous gold, an AgAu bimetallic catalyst. We use microscopy and digital reconstruction to obtain the morphology of a two-dimensional slice of a nanoporous gold sample. Using lattice Boltzmann fluid dynamics simulations along with thermodynamic models based on first-principles total-energy calculations, we show that some sections of this sample have low local O2 partial pressures when exposed to reaction conditions, which leads to a pure Au surface in these regions, instead of the active bimetallic AgAu phase. We also explore the effect of temperature on the surface structure and find that moderate temperatures (≈300–450 K) should result in the highest intrinsic catalytic performance, in apparent agreement with experimental results.},
doi = {10.1063/1.4984614},
journal = {Journal of Chemical Physics},
number = 21,
volume = 146,
place = {United States},
year = {Thu Jun 01 00:00:00 EDT 2017},
month = {Thu Jun 01 00:00:00 EDT 2017}
}

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Works referenced in this record:

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts
journal, December 2016

  • Zugic, Branko; Wang, Lucun; Heine, Christian
  • Nature Materials, Vol. 16, Issue 5
  • DOI: 10.1038/nmat4824

Revealing the Distribution of the Atoms within Individual Bimetallic Catalyst Nanoparticles
journal, August 2014

  • Felfer, Peter; Benndorf, Paul; Masters, Anthony
  • Angewandte Chemie International Edition, Vol. 53, Issue 42
  • DOI: 10.1002/anie.201405043

Correlating Catalytic Activity of Ag–Au Nanoparticles with 3D Compositional Variations
journal, March 2014

  • Slater, Thomas J. A.; Macedo, Alexandra; Schroeder, Sven L. M.
  • Nano Letters, Vol. 14, Issue 4
  • DOI: 10.1021/nl4047448

Silver-rich clusters in nanoporous gold
journal, January 2017


Resolved-particle fixed bed CFD with microkinetics for ethylene oxidation
journal, July 2016

  • Partopour, Behnam; Dixon, Anthony G.
  • AIChE Journal, Vol. 63, Issue 1
  • DOI: 10.1002/aic.15422

CO oxidation by co-adsorbed atomic O on the Au(321) surface with Ag impurities: A mechanistic study from first-principles calculations
journal, February 2012


The lattice Boltzmann equation: theory and applications
journal, December 1992


Publisher's Note: Lattice Boltzmann approach for complex nonequilibrium flows [Phys. Rev. E 92 , 043308 (2015)]
journal, December 2015


Evolution of Catalytic Activity of Au−Ag Bimetallic Nanoparticles on Mesoporous Support for CO Oxidation
journal, October 2005

  • Wang, Ai-Qin; Chang, Chun-Ming; Mou, Chung-Yuan
  • The Journal of Physical Chemistry B, Vol. 109, Issue 40
  • DOI: 10.1021/jp051530q

Chemisorbed Oxygen on the Au(321) Surface Alloyed with Silver: A First-Principles Investigation
journal, April 2015

  • Moskaleva, Lyudmila V.; Weiss, Theodor; Klüner, Thorsten
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/jp511884k

Silver residues as a possible key to a remarkable oxidative catalytic activity of nanoporous gold
journal, January 2011

  • Moskaleva, Lyudmila V.; Röhe, Sarah; Wittstock, Arne
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 10
  • DOI: 10.1039/c0cp02372h

Mesoscopic Modeling of Slip Motion at Fluid-Solid Interfaces with Heterogeneous Catalysis
journal, July 2002


Phase diagrams for surface alloys
journal, September 1997


Synergistic Effect in an Au−Ag Alloy Nanocatalyst:  CO Oxidation
journal, January 2005

  • Liu, Jun-Hong; Wang, Ai-Qin; Chi, Yu-Shan
  • The Journal of Physical Chemistry B, Vol. 109, Issue 1
  • DOI: 10.1021/jp044938g

Surface enrichment in AgAu alloys
journal, September 1976


Three-dimensional computational analysis of transport phenomena in a PEM fuel cell—a parametric study
journal, November 2003


Alloys in catalysis: phase separation and surface segregation phenomena in response to the reactive environment
journal, January 2012

  • Zafeiratos, Spiros; Piccinin, Simone; Teschner, Detre
  • Catalysis Science & Technology, Vol. 2, Issue 9
  • DOI: 10.1039/c2cy00487a

Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure
journal, December 2001


On the theoretical understanding of the unexpected O 2 activation by nanoporous gold
journal, January 2011

  • Fajín, José L. C.; Cordeiro, M. Natália D. S.; Gomes, José R. B.
  • Chem. Commun., Vol. 47, Issue 29
  • DOI: 10.1039/c1cc12166a

Catalysis on nanoporous gold–silver systems: Synergistic effects toward oxidation reactions and influence of the surface composition
journal, March 2014


Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface
journal, March 2014

  • Xu, Bingjun; Siler, Cassandra G. F.; Madix, Robert J.
  • Chemistry - A European Journal, Vol. 20, Issue 16
  • DOI: 10.1002/chem.201304837

The ImageJ ecosystem: An open platform for biomedical image analysis: T
journal, July 2015

  • Schindelin, Johannes; Rueden, Curtis T.; Hiner, Mark C.
  • Molecular Reproduction and Development, Vol. 82, Issue 7-8
  • DOI: 10.1002/mrd.22489

Surface Composition Control of the Binary Au–Ag Catalyst for Enhanced Oxidant-Free Dehydrogenation
journal, September 2016


A multiregion operator-splitting CFD approach for coupling microkinetic modeling with internal porous transport in heterogeneous catalytic reactors
journal, January 2016

  • Maffei, Tiziano; Gentile, Giancarlo; Rebughini, Stefano
  • Chemical Engineering Journal, Vol. 283
  • DOI: 10.1016/j.cej.2015.08.080

Ab Initio Thermodynamics and First-Principles Microkinetics for Surface Catalysis
journal, January 2016


Core−Shell (Ag)Au Bimetallic Nanoparticles:  Analysis of Transmission Electron Microscopy Images
journal, December 2000

  • Srnová-Šloufová, Ivana; Lednický, František; Gemperle, Antonín
  • Langmuir, Vol. 16, Issue 25
  • DOI: 10.1021/la0009588

Direct numerical calculation of the kinematic tortuosity of reactive mixture flow in the anode layer of solid oxide fuel cells by the lattice Boltzmann method
journal, July 2007


Comparison of surface structure and segregation in AgAu and NiPd alloys
journal, September 2004


Wavelet-based surrogate time series for multiscale simulation of heterogeneous catalysis
journal, April 2016


Structure of Gold–Silver Nanoparticles
journal, January 2017

  • Godfrey, Ian J.; Dent, Andrew J.; Parkin, Ivan P.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 3
  • DOI: 10.1021/acs.jpcc.6b11186

Segregation and sputter effects on perfectly smooth (111) and (100) surfaces of AuAg alloys studied by AES
journal, March 1988


Nanoporous Au: An Unsupported Pure Gold Catalyst?
journal, March 2009

  • Wittstock, Arne; Neumann, Björn; Schaefer, Andreas
  • The Journal of Physical Chemistry C, Vol. 113, Issue 14
  • DOI: 10.1021/jp808185v

Lattice Boltzmann 2038
journal, March 2015


Bulk and surface characterization of supported AgAu alloy catalysts
journal, January 1988


Lattice Boltzmann pore-scale model for multicomponent reactive transport in porous media: MULTICOMPONENT REACTIVE TRANSPORT
journal, May 2006

  • Kang, Qinjun; Lichtner, Peter C.; Zhang, Dongxiao
  • Journal of Geophysical Research: Solid Earth, Vol. 111, Issue B5
  • DOI: 10.1029/2005JB003951

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Mapping reactive flow patterns in monolithic nanoporous catalysts
journal, July 2016

  • Falcucci, Giacomo; Succi, Sauro; Montessori, Andrea
  • Microfluidics and Nanofluidics, Vol. 20, Issue 7
  • DOI: 10.1007/s10404-016-1767-5

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions
journal, November 2016


How Does Nanoporous Gold Dissociate Molecular Oxygen?
journal, July 2016

  • Montemore, Matthew M.; Madix, Robert J.; Kaxiras, Efthimios
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b03371

Modeling and Numerical Studies for a 3D Two-Phase Mixed-Domain Model of PEM Fuel Cell
journal, January 2013

  • He, Mingyan; Huang, Ziping; Sun, Pengtao
  • Journal of The Electrochemical Society, Vol. 160, Issue 4
  • DOI: 10.1149/2.036304jes

In situ adaptive tabulation for the CFD simulation of heterogeneous reactors based on operator-splitting algorithm
journal, August 2016

  • Bracconi, Mauro; Maestri, Matteo; Cuoci, Alberto
  • AIChE Journal, Vol. 63, Issue 1
  • DOI: 10.1002/aic.15441

Alloy Catalyst in a Reactive Environment: The Example of Ag-Cu Particles for Ethylene Epoxidation
journal, January 2010


Electrum, the Gold–Silver Alloy, from the Bulk Scale to the Nanoscale: Synthesis, Properties, and Segregation Rules
journal, November 2015

  • Guisbiers, Grégory; Mendoza-Cruz, Rubén; Bazán-Díaz, Lourdes
  • ACS Nano, Vol. 10, Issue 1
  • DOI: 10.1021/acsnano.5b05755

Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature
journal, January 2010


Promotion of CO Oxidation on Bimetallic Au−Ag(110) Surfaces: A Combined Microscopic and Theoretical Study
journal, July 2009

  • Chou, Jyh-Pin; Pai, Woei Wu; Kuo, Ching-Chang
  • The Journal of Physical Chemistry C, Vol. 113, Issue 30
  • DOI: 10.1021/jp811238w

Research on unsupported nanoporous gold catalyst for CO oxidation
journal, December 2007


Nanoporous Gold by Alloy Corrosion: Method-Structure-Property Relationships
journal, January 2017

  • Graf, M.; Roschning, B.; Weissmüller, J.
  • Journal of The Electrochemical Society, Vol. 164, Issue 4
  • DOI: 10.1149/2.1681704jes

Interaction of Oxygen with Supported Ag–Au Alloy Catalysts
journal, February 1996

  • Kondarides, Dimitris I.; Verykios, Xenophon E.
  • Journal of Catalysis, Vol. 158, Issue 2
  • DOI: 10.1006/jcat.1996.0038

Controlling O coverage and stability by alloying Au and Ag
journal, January 2016

  • Montemore, Matthew M.; Cubuk, Ekin D.; Klobas, J. Eric
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/c6cp05611c

Effects of Knudsen diffusivity on the effective reactivity of nanoporous catalyst media
journal, November 2016


Gold Catalysts: Nanoporous Gold Foams
journal, December 2006

  • Zielasek, Volkmar; Jürgens, Birte; Schulz, Christian
  • Angewandte Chemie International Edition, Vol. 45, Issue 48
  • DOI: 10.1002/anie.200602484

A novel efficient Au–Ag alloy catalyst system: preparation, activity, and characterization
journal, July 2005


The O, OH and OOH-assisted selective coupling of methanol on Au–Ag(111)
journal, January 2016

  • Zhong, Wenhui; Liang, Jinxia; Hu, Wei
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 15
  • DOI: 10.1039/c6cp00336b

Selective oxidation of methanol to methyl formate on catalysts of Au–Ag alloy nanoparticles supported on titania under UV irradiation
journal, January 2014

  • Han, Chenhui; Yang, Xuzhuang; Gao, Guanjun
  • Green Chem., Vol. 16, Issue 7
  • DOI: 10.1039/c4gc00367e

Lattice Boltzmann simulation of catalytic reactions
journal, October 2008


Low Temperature CO Oxidation over Unsupported Nanoporous Gold
journal, January 2007

  • Xu, Caixia; Su, Jixin; Xu, Xiaohong
  • Journal of the American Chemical Society, Vol. 129, Issue 1, p. 42-43
  • DOI: 10.1021/ja0675503

High-pressure operando STM studies giving insight in CO oxidation and NO reduction over Pt(110)
journal, April 2015


A pyramid approach to subpixel registration based on intensity
journal, January 1998

  • Thevenaz, P.; Ruttimann, U. E.; Unser, M.
  • IEEE Transactions on Image Processing, Vol. 7, Issue 1
  • DOI: 10.1109/83.650848

Computationally efficient incorporation of microkinetics into resolved-particle CFD simulations of fixed-bed reactors
journal, May 2016


Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation
journal, June 2015


Atomic origins of the high catalytic activity of nanoporous gold
journal, August 2012

  • Fujita, Takeshi; Guan, Pengfei; McKenna, Keith
  • Nature Materials, Vol. 11, Issue 9
  • DOI: 10.1038/nmat3391

Lattice-Boltzmann Method for Complex Flows
journal, January 2010


Works referencing / citing this record:

Capillarity-Driven Oil Flow in Nanopores: Darcy Scale Analysis of Lucas–Washburn Imbibition Dynamics
journal, August 2018


Simulating Engineering Flows through Complex Porous Media via the Lattice Boltzmann Method
journal, March 2018


Stress-Dependent Pore Deformation Effects on Multiphase Flow Properties of Porous Media
journal, October 2019


Lattice Boltzmann Simulation of the Hydrodynamic Entrance Region of Rectangular Microchannels in the Slip Regime
journal, February 2018

  • Ma, Niya; Duan, Zhipeng; Ma, Hao
  • Micromachines, Vol. 9, Issue 2
  • DOI: 10.3390/mi9020087