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Title: Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts

Abstract

Effective catalysts stabilize specific transition states and control the transport of species to and from catalytically active sites. Enzymes show these traits thanks to their diverse amino acid functional groups encapsulating metal centres, but are limited in the reaction conditions in which they can operate. Realizing a catalyst with this kinetic and transport control that can be used under demanding industrial conditions is challenging. Here, we show a modular approach for the systematic synthesis of polymer–nanocrystal hybrids, where palladium nanocrystals are encapsulated within tunable microporous polymer layers. The polymer chemistry and morphology control the catalytic performance of the metal sites, affecting the transition state for CO oxidation and controlling the transport of CO2 away from the active site. In conclusion, this approach can be applied to other polymer–nanocrystal compositions and catalytic applications, and is therefore expected to have an impact in many areas of catalysis.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [1];  [3];  [1]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Stanford Univ., Stanford, CA (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1576519
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Riscoe, Andrew R., Wrasman, Cody J., Herzing, Andrew A., Hoffman, Adam S., Menon, Aditya, Boubnov, Alexey, Vargas, Maria, Bare, Simon R., and Cargnello, Matteo. Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts. United States: N. p., 2019. Web. doi:10.1038/s41929-019-0322-7.
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Riscoe, Andrew R., Wrasman, Cody J., Herzing, Andrew A., Hoffman, Adam S., Menon, Aditya, Boubnov, Alexey, Vargas, Maria, Bare, Simon R., & Cargnello, Matteo. Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts. United States. https://doi.org/10.1038/s41929-019-0322-7
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Riscoe, Andrew R., Wrasman, Cody J., Herzing, Andrew A., Hoffman, Adam S., Menon, Aditya, Boubnov, Alexey, Vargas, Maria, Bare, Simon R., and Cargnello, Matteo. Mon . "Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts". United States. https://doi.org/10.1038/s41929-019-0322-7. https://www.osti.gov/servlets/purl/1576519.
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@article{osti_1576519,
title = {Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts},
author = {Riscoe, Andrew R. and Wrasman, Cody J. and Herzing, Andrew A. and Hoffman, Adam S. and Menon, Aditya and Boubnov, Alexey and Vargas, Maria and Bare, Simon R. and Cargnello, Matteo},
abstractNote = {Effective catalysts stabilize specific transition states and control the transport of species to and from catalytically active sites. Enzymes show these traits thanks to their diverse amino acid functional groups encapsulating metal centres, but are limited in the reaction conditions in which they can operate. Realizing a catalyst with this kinetic and transport control that can be used under demanding industrial conditions is challenging. Here, we show a modular approach for the systematic synthesis of polymer–nanocrystal hybrids, where palladium nanocrystals are encapsulated within tunable microporous polymer layers. The polymer chemistry and morphology control the catalytic performance of the metal sites, affecting the transition state for CO oxidation and controlling the transport of CO2 away from the active site. In conclusion, this approach can be applied to other polymer–nanocrystal compositions and catalytic applications, and is therefore expected to have an impact in many areas of catalysis.},
doi = {10.1038/s41929-019-0322-7},
journal = {Nature Catalysis},
number = 10,
volume = 2,
place = {United States},
year = {2019},
month = {8}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s41929-019-0322-7
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Cited by: 9 works
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Figures / Tables:

Fig. 1 Fig. 1: Modular synthesis of the Pd/polymer composites. a, Stepwise scheme depicting the synthetic procedure to encapsulate NCs within polymer layers (POFs). From left to right: Pd NCs and POF are synthesized separately, according to the literature, with melamine and terephthaldehyde. The Pd NCs are attached to the POF surfacemore » via van der Waals forces, then stabilizing ligands are removed from the Pd surface using a thermal air treatment. Finally, additional polymer growth is performed in the presence of the Pd/POF material. b-e, Representative TEM images for each step in a during the course of the synthetic protocol: NCs (b); 3% by weight Pd/POF (c); the same sample of 3% by weight Pd/POF after thermal treatment (d); 3% by weight Pd/POF encapsulated in additional POF, resulting in 1% Pd POF/Pd/POF (e). f-i, Particle size distributions calculated from TEM images of the Pd NCs at each corresponding step (b-e) of the synthesis (minimum number of particles counted N= 150).« less
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Works referenced in this record:

Selective Oxidation of Methane by the Bis(μ-oxo)dicopper Core Stabilized on ZSM-5 and Mordenite Zeolites
journal, February 2005

  • Groothaert, Marijke H.; Smeets, Pieter J.; Sels, Bert F.
  • Journal of the American Chemical Society, Vol. 127, Issue 5
  • DOI: 10.1021/ja047158u

Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters
journal, March 2011

  • Allian, Ayman D.; Takanabe, Kazuhiro; Fujdala, Kyle L.
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja110073u

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Homogeneous, heterogeneous, and enzymatic catalysis
journal, September 1988

  • Oyama, S. Ted; Somorjai, Gabor A.
  • Journal of Chemical Education, Vol. 65, Issue 9
  • DOI: 10.1021/ed065p765

Quantum Mechanical Basis for Kinetic Diameters of Small Gaseous Molecules
journal, January 2014

  • Mehio, Nada; Dai, Sheng; Jiang, De-en
  • The Journal of Physical Chemistry A, Vol. 118, Issue 6
  • DOI: 10.1021/jp412588f

Controlled selectivity for palladium catalysts using self-assembled monolayers
journal, September 2010

  • Marshall, Stephen T.; O’Brien, Marykate; Oetter, Brittany
  • Nature Materials, Vol. 9, Issue 10
  • DOI: 10.1038/nmat2849

Catalyst-free Preparation of Melamine-Based Microporous Polymer Networks through Schiff Base Chemistry
journal, June 2009

  • Schwab, Matthias Georg; Fassbender, Birgit; Spiess, Hans Wolfgang
  • Journal of the American Chemical Society, Vol. 131, Issue 21
  • DOI: 10.1021/ja902116f

Surface diffusion of strong adsorbing vapours on porous carbon
journal, January 2002

Cooperative effects in heterogeneous catalysis. Part 2.—Analysis and modelling of the temperature dependence of the oscillating catalytic oxidation of CO on a palladium Al2O3-supported catalyst
journal, January 1988

  • Plath, Peter J.; Möller, Karin; Jaeger, Nils I.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 84, Issue 6
  • DOI: 10.1039/f19888401751

CO Oxidation as a Prototypical Reaction for Heterogeneous Processes
journal, September 2011

  • Freund, Hans-Joachim; Meijer, Gerard; Scheffler, Matthias
  • Angewandte Chemie International Edition, Vol. 50, Issue 43
  • DOI: 10.1002/anie.201101378

An infrared and kinetic study of carbon monoxide oxidation on model silica-supported palladium catalysts from 10-9 to 15 Torr
journal, July 1993

  • Xu, Xueping; Goodman, D. Wayne
  • The Journal of Physical Chemistry, Vol. 97, Issue 29
  • DOI: 10.1021/j100131a047

Visualization of oscillatory behaviour of Pt nanoparticles catalysing CO oxidation
journal, July 2014

  • Vendelbo, S. B.; Elkjær, C. F.; Falsig, H.
  • Nature Materials, Vol. 13, Issue 9
  • DOI: 10.1038/nmat4033

In Situ XAS Investigations of Chemical Oscillations in the Oxidation of Co on Supported Pd Catalysts
journal, April 1997

  • Ressler, T.; Hagelstein, M.; Hatje, U.
  • Le Journal de Physique IV, Vol. 7, Issue C2
  • DOI: 10.1051/jp4:1997221

Functionalization of Platinum Nanoparticles with l -Proline: Simultaneous Enhancements of Catalytic Activity and Selectivity
journal, January 2015

  • Schrader, Imke; Warneke, Jonas; Backenköhler, Jana
  • Journal of the American Chemical Society, Vol. 137, Issue 2
  • DOI: 10.1021/ja511349p

Surface Diffusion of Adsorbed Molecules in Porous Media:  Monolayer, Multilayer, and Capillary Condensation Regimes
journal, September 2001

  • Choi, Jeong-Gil; Do, D. D.; Do, H. D.
  • Industrial & Engineering Chemistry Research, Vol. 40, Issue 19
  • DOI: 10.1021/ie010195z

Copolymerization of terephthalaldehyde with pyrrole, indole and carbazole gives microporous POFs functionalized with unpaired electrons
journal, January 2013

  • Katsoulidis, Alexandros P.; Dyar, Scott M.; Carmieli, Raanan
  • Journal of Materials Chemistry A, Vol. 1, Issue 35
  • DOI: 10.1039/c3ta11934c

Exceptional Activity for Methane Combustion over Modular Pd@CeO2 Subunits on Functionalized Al2O3
journal, August 2012

Diffusion‐induced instability in chemically reacting systems: Steady‐state multiplicity, oscillation, and chaos
journal, July 1991

  • Lengyel, István; Epstein, Irving R.
  • Chaos: An Interdisciplinary Journal of Nonlinear Science, Vol. 1, Issue 1
  • DOI: 10.1063/1.165819

Surface diffusion of adsorbable gases through porous media
journal, January 1972

New design paradigm for heterogeneous catalysts
journal, April 2015

  • Vojvodic, Aleksandra; Nørskov, Jens K.
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv023

Molecular imprinting of bulk, microporous silica
journal, January 2000

  • Katz, Alexander; Davis, Mark E.
  • Nature, Vol. 403, Issue 6767, p. 286-289
  • DOI: 10.1038/35002032

Metal–organic frameworks as selectivity regulators for hydrogenation reactions
journal, October 2016

Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry
journal, January 2003

  • Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain
  • Angewandte Chemie International Edition, Vol. 42, Issue 2, p. 156-181
  • DOI: 10.1002/anie.200390072

Diffusion on Surfaces. I. Effect of Concentration on the Diffusivity of Physically Adsorbed Gases
journal, May 1974

  • Gilliland, Edwin R.; Baddour, Raymond F.; Perkinson, George P.
  • Industrial & Engineering Chemistry Fundamentals, Vol. 13, Issue 2
  • DOI: 10.1021/i160050a001

Confining Functional Nanoparticles into Colloidal Imine-Based COF Spheres by a Sequential Encapsulation-Crystallization Method
journal, June 2017

  • Rodríguez-San-Miguel, David; Yazdi, Amirali; Guillerm, Vincent
  • Chemistry - A European Journal, Vol. 23, Issue 36
  • DOI: 10.1002/chem.201702072

Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids
journal, February 1979

scikit-image: image processing in Python
journal, January 2014

  • van der Walt, Stéfan; Schönberger, Johannes L.; Nunez-Iglesias, Juan
  • PeerJ, Vol. 2
  • DOI: 10.7717/peerj.453

Trends in the Catalytic CO Oxidation Activity of Nanoparticles
journal, June 2008

  • Falsig, Hanne; Hvolbæk, Britt; Kristensen, Iben S.
  • Angewandte Chemie International Edition, Vol. 47, Issue 26
  • DOI: 10.1002/anie.200801479

Enhancement of CO 2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification
journal, January 2014

  • Mason, Christopher R.; Maynard-Atem, Louise; Heard, Kane W. J.
  • Macromolecules, Vol. 47, Issue 3
  • DOI: 10.1021/ma401869p

Oscillatory Kinetics in Heterogeneous Catalysis
journal, May 1995

Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy
journal, January 2009

Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion
journal, October 2017

  • Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis
  • ACS Catalysis, Vol. 7, Issue 11
  • DOI: 10.1021/acscatal.7b02414

Vibrational Predissociation Spectrum of the Carbamate Radical Anion, C 5 H 5 N-CO 2 − , Generated by Reaction of Pyridine with (CO 2 ) m −
journal, November 2010

  • Kamrath, Michael Z.; Relph, Rachael A.; Johnson, Mark A.
  • Journal of the American Chemical Society, Vol. 132, Issue 44
  • DOI: 10.1021/ja1073036

A Ship-in-a-Bottle Strategy To Synthesize Encapsulated Intermetallic Nanoparticle Catalysts: Exemplified for Furfural Hydrogenation
journal, February 2016

Fast and flexible X-ray tomography using the ASTRA toolbox
journal, January 2016

  • van Aarle, Wim; Palenstijn, Willem Jan; Cant, Jeroen
  • Optics Express, Vol. 24, Issue 22
  • DOI: 10.1364/OE.24.025129

A model for surface diffusion of ethane and propane in activated carbon
journal, September 1996

Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation
journal, February 2012

  • Lu, Guang; Li, Shaozhou; Guo, Zhen
  • Nature Chemistry, Vol. 4, Issue 4, p. 310-316
  • DOI: 10.1038/nchem.1272

Transmission and fluorescence X-ray absorption spectroscopy cell/flow reactor for powder samples under vacuum or in reactive atmospheres
journal, July 2016

  • Hoffman, A. S.; Debefve, L. M.; Bendjeriou-Sedjerari, A.
  • Review of Scientific Instruments, Vol. 87, Issue 7
  • DOI: 10.1063/1.4958824

Multiple-scattering calculations of x-ray-absorption spectra
journal, July 1995

Identification of the Basic Sites on Nitrogen-Substituted Microporous and Mesoporous Silicate Frameworks Using CO 2 as a Probe Molecule
journal, January 2018

Supported Dendrimer-Encapsulated Metal Clusters: Toward Heterogenizing Homogeneous Catalysts
journal, July 2017

  • Ye, Rong; Zhukhovitskiy, Aleksandr V.; Deraedt, Christophe V.
  • Accounts of Chemical Research, Vol. 50, Issue 8
  • DOI: 10.1021/acs.accounts.7b00232

Highly Enhanced Selectivity and Easy Regeneration for the Separation of CO 2 over N 2 on Melamine-Based Microporous Organic Polymers
journal, July 2014

  • Hu, Jing-Xiu; Shang, Hao; Wang, Jin-Gui
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 29
  • DOI: 10.1021/ie501736t

"Artificial enzyme" combining a metal catalytic group and a hydrophobic binding cavity
journal, February 1970

  • Breslow, Ronald.; Overman, Larry E.
  • Journal of the American Chemical Society, Vol. 92, Issue 4
  • DOI: 10.1021/ja00707a062

Preparation of Cu Nanoclusters within Dendrimer Templates
journal, May 1998

  • Zhao, Mingqi; Sun, Li; Crooks, Richard M.
  • Journal of the American Chemical Society, Vol. 120, Issue 19
  • DOI: 10.1021/ja980438n

Chromatographic study of surface diffusion
journal, November 1968

The Roles of Entropy and Enthalpy in Stabilizing Ion-Pairs at Transition States in Zeolite Acid Catalysis
journal, August 2011

  • Gounder, Rajamani; Iglesia, Enrique
  • Accounts of Chemical Research, Vol. 45, Issue 2
  • DOI: 10.1021/ar200138n

A Threshold Selection Method from Gray-Level Histograms
journal, January 1979

The ASTRA Toolbox: A platform for advanced algorithm development in electron tomography
journal, October 2015

Efficient Removal of Organic Ligands from Supported Nanocrystals by Fast Thermal Annealing Enables Catalytic Studies on Well-Defined Active Phases
journal, May 2015

  • Cargnello, Matteo; Chen, Chen; Diroll, Benjamin T.
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b03333

Classical kinetics of catalytic reactions
journal, May 2003

Trends in the Catalytic CO Oxidation Activity of Nanoparticles
journal, June 2008

  • Falsig, Hanne; Hvolbæk, Britt; Kristensen, Iben S.
  • Angewandte Chemie, Vol. 120, Issue 26
  • DOI: 10.1002/ange.200801479

Homogeneous and Heterogeneous Catalysis: Bridging the Gap Through Surface Organometallic Chemistry
journal, April 2003

  • Coperet, Christophe; Chabanas, Mathieu; Saint-Arroman, Romain Petroff
  • ChemInform, Vol. 34, Issue 16
  • DOI: 10.1002/chin.200316246

Classical Kinetics of Catalytic Reactions
journal, August 2003

The chemical basis of morphogenesis
journal, January 1990

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