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Title: Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

Abstract

Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. Lastly, these results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5];  [6];  [7];  [3];  [4];  [5];  [2];  [5];  [6];  [5];  [4];  [3];  [3];  [3];  [2];  [8] more »; ORCiD logo [1] « less
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  5. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  6. Clemson Univ., SC (United States). Chemical and Biomolecular Engineering
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1433888
Alternate Identifier(s):
OSTI ID: 1415321
Grant/Contract Number:  
AC02-06CH11357; SC0012702
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 57; Journal Issue: 4; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; atomic layer deposition (ALD); heterogeneous catalysis; metal-organic framworks (MOFs); platinum; sinter-resistance

Citation Formats

Kim, In Soo, Li, Zhanyong, Zheng, Jian, Platero-Prats, Ana E., Mavrandonakis, Andreas, Pellizzeri, Steven, Ferrandon, Magali, Vjunov, Aleksei, Gallington, Leighanne C., Webber, Thomas E., Vermeulen, Nicolaas A., Penn, R. Lee, Getman, Rachel B., Cramer, Christopher J., Chapman, Karena W., Camaioni, Donald M., Fulton, John L., Lercher, Johannes A., Farha, Omar K., Hupp, Joseph T., and Martinson, Alex B. F. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework. United States: N. p., 2018. Web. doi:10.1002/anie.201708092.
Kim, In Soo, Li, Zhanyong, Zheng, Jian, Platero-Prats, Ana E., Mavrandonakis, Andreas, Pellizzeri, Steven, Ferrandon, Magali, Vjunov, Aleksei, Gallington, Leighanne C., Webber, Thomas E., Vermeulen, Nicolaas A., Penn, R. Lee, Getman, Rachel B., Cramer, Christopher J., Chapman, Karena W., Camaioni, Donald M., Fulton, John L., Lercher, Johannes A., Farha, Omar K., Hupp, Joseph T., & Martinson, Alex B. F. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework. United States. doi:10.1002/anie.201708092.
Kim, In Soo, Li, Zhanyong, Zheng, Jian, Platero-Prats, Ana E., Mavrandonakis, Andreas, Pellizzeri, Steven, Ferrandon, Magali, Vjunov, Aleksei, Gallington, Leighanne C., Webber, Thomas E., Vermeulen, Nicolaas A., Penn, R. Lee, Getman, Rachel B., Cramer, Christopher J., Chapman, Karena W., Camaioni, Donald M., Fulton, John L., Lercher, Johannes A., Farha, Omar K., Hupp, Joseph T., and Martinson, Alex B. F. Tue . "Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework". United States. doi:10.1002/anie.201708092. https://www.osti.gov/servlets/purl/1433888.
@article{osti_1433888,
title = {Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework},
author = {Kim, In Soo and Li, Zhanyong and Zheng, Jian and Platero-Prats, Ana E. and Mavrandonakis, Andreas and Pellizzeri, Steven and Ferrandon, Magali and Vjunov, Aleksei and Gallington, Leighanne C. and Webber, Thomas E. and Vermeulen, Nicolaas A. and Penn, R. Lee and Getman, Rachel B. and Cramer, Christopher J. and Chapman, Karena W. and Camaioni, Donald M. and Fulton, John L. and Lercher, Johannes A. and Farha, Omar K. and Hupp, Joseph T. and Martinson, Alex B. F.},
abstractNote = {Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. Lastly, these results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.},
doi = {10.1002/anie.201708092},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 4,
volume = 57,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 20 works
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Figures / Tables:

Figure 1. Figure 1.: Idealized structure of NU-1000, highlighting meso- and microporous channels and zirconia-like nodes with –OH and –OH2 groups. Side view shows the location of non-channel-like pores that interconnect the material’s 1D channels.

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Works referenced in this record:

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

DFT Study of the Hydrogen Spillover Mechanism on Pt-Doped Graphite
journal, July 2009

  • Psofogiannakis, George M.; Froudakis, George E.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 33
  • DOI: 10.1021/jp902987s

Atomic Layer Deposition of Pt Nanoparticles within the Cages of MIL-101: A Mild and Recyclable Hydrogenation Catalyst
journal, March 2016

  • Leus, Karen; Dendooven, Jolien; Tahir, Norini
  • Nanomaterials, Vol. 6, Issue 3
  • DOI: 10.3390/nano6030045

Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework
journal, February 2016

  • Li, Zhanyong; Schweitzer, Neil M.; League, Aaron B.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12515

Structural Transitions of the Metal-Oxide Nodes within Metal–Organic Frameworks: On the Local Structures of NU-1000 and UiO-66
journal, March 2016

  • Platero-Prats, Ana E.; Mavrandonakis, Andreas; Gallington, Leighanne C.
  • Journal of the American Chemical Society, Vol. 138, Issue 12
  • DOI: 10.1021/jacs.6b00069

Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000
journal, January 2017

  • Platero-Prats, Ana E.; Li, Zhanyong; Gallington, Leighanne C.
  • Faraday Discussions, Vol. 201
  • DOI: 10.1039/C7FD00110J

Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
journal, October 2013

  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804
  • DOI: 10.1021/ja408959g

A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction
journal, January 2016

  • Hauser, Andreas W.; Horn, Paul R.; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C6CP00360E

Shape-controlled synthesis of platinum nanocrystals for catalytic and electrocatalytic applications
journal, February 2009


Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000
journal, December 2015

  • Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo
  • Nature Protocols, Vol. 11, Issue 1
  • DOI: 10.1038/nprot.2016.001

Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature
journal, November 2016


Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012

  • Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben
  • Angewandte Chemie, Vol. 124, Issue 20
  • DOI: 10.1002/ange.201108565

Hybrid porous solids past, present, future
journal, January 2008

  • Férey, Gérard
  • Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
  • DOI: 10.1039/B618320B

Catalytic Combustion and Dehydrogenation Reactions during Atomic Layer Deposition of Platinum
journal, May 2012

  • Mackus, Adriaan J. M.; Leick, Noémi; Baker, Layton
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm203812v

Temperature-dependent EXAFS analysis of embedded Pt nanocrystals
journal, March 2009


Subnanometer-sized Pt/Sn alloy cluster catalysts for the dehydrogenation of linear alkanes
journal, January 2013

  • Hauser, Andreas W.; Gomes, Joseph; Bajdich, Michal
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 47
  • DOI: 10.1039/c3cp53796j

Heterogeneous Catalytic Hydrogenation: Is Double Bond/Surface Coordination Necessary?
journal, November 2009

  • Delbecq, Françoise; Loffreda, David; Sautet, Philippe
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 1
  • DOI: 10.1021/jz900159q

Density Functional Study of Ethylene Hydrogenation on Pt(111) Surface
journal, July 2000

  • Miura, Toshiko; Kobayashi, Hisayoshi; Domen, Kazunari
  • The Journal of Physical Chemistry B, Vol. 104, Issue 29
  • DOI: 10.1021/jp993425k

Stable Metal–Organic Framework-Supported Niobium Catalysts
journal, October 2016


Chemical, thermal and mechanical stabilities of metal–organic frameworks
journal, February 2016


Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

Kinetic Regimes in Ethylene Hydrogenation over Transition-Metal Surfaces
journal, April 2016


Regioselective Atomic Layer Deposition in Metal–Organic Frameworks Directed by Dispersion Interactions
journal, October 2016

  • Gallington, Leighanne C.; Kim, In Soo; Liu, Wei-Guang
  • Journal of the American Chemical Society, Vol. 138, Issue 41
  • DOI: 10.1021/jacs.6b08711

Formkontrolle bei der Synthese von Metallnanokristallen: einfache Chemie, komplexe Physik?
journal, December 2008


Atomic Layer Deposition of Ir−Pt Alloy Films
journal, April 2010

  • Christensen, Steven T.; Elam, Jeffrey W.
  • Chemistry of Materials, Vol. 22, Issue 8, p. 2517-2525
  • DOI: 10.1021/cm9031978

Atomic Layer Deposition of Platinum Thin Films
journal, May 2003

  • Aaltonen, Titta; Ritala, Mikko; Sajavaara, Timo
  • Chemistry of Materials, Vol. 15, Issue 9, p. 1924-1928
  • DOI: 10.1021/cm021333t

Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012

  • Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben
  • Angewandte Chemie International Edition, Vol. 51, Issue 20
  • DOI: 10.1002/anie.201108565

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition
journal, June 2015


Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy
journal, July 2009

  • Kessels, W. M. M.; Knoops, H. C. M.; Dielissen, S. A. F.
  • Applied Physics Letters, Vol. 95, Issue 1
  • DOI: 10.1063/1.3176946

Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000
journal, October 2014

  • Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723
  • DOI: 10.1021/jz501899j

Estimation of mean size and shape of small metal particles by EXAFS
journal, January 1999

  • Jentys, Andreas
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 17
  • DOI: 10.1039/a904654b

DFT Study of Hydrogen Storage by Spillover on Graphite with Oxygen Surface Groups
journal, October 2009

  • Psofogiannakis, George M.; Froudakis, George E.
  • Journal of the American Chemical Society, Vol. 131, Issue 42
  • DOI: 10.1021/ja906159p

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
journal, May 2013

  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297
  • DOI: 10.1021/ja4050828

Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane
journal, February 2009

  • Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P.
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2384

Theoretical analysis of hydrogen spillover mechanism on carbon nanotubes
journal, February 2015

  • Juarez-Mosqueda, Rosalba; Mavrandonakis, Andreas; Kuc, Agnieszka B.
  • Frontiers in Chemistry, Vol. 3
  • DOI: 10.3389/fchem.2015.00002

Soft porous crystals
journal, November 2009

  • Horike, Satoshi; Shimomura, Satoru; Kitagawa, Susumu
  • Nature Chemistry, Vol. 1, Issue 9, p. 695-704
  • DOI: 10.1038/nchem.444

Watching Nanoparticles Grow:  The Mechanism and Kinetics for the Formation of TiO 2 -Supported Platinum Nanoparticles
journal, November 2007

  • Chupas, Peter J.; Chapman, Karena W.; Jennings, Guy
  • Journal of the American Chemical Society, Vol. 129, Issue 45
  • DOI: 10.1021/ja076437p

Application of high-energy X-rays and Pair-Distribution-Function analysis to nano-scale structural studies in catalysis
journal, July 2009


    Works referencing / citing this record:

    Cobalt-bridged secondary building units in a titanium metal–organic framework catalyze cascade reduction of N-heteroarenes
    journal, January 2019

    • Feng, Xuanyu; Song, Yang; Chen, Justin S.
    • Chemical Science, Vol. 10, Issue 7
    • DOI: 10.1039/c8sc04610g

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.