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Title: Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches

Abstract

Alloy nanoparticle catalysts are known to afford unique activities that can differ markedly from their parent metals, but there remains a generally limited understanding of the nature of their atomic (and likely dynamic) structures as exist in heterogeneously supported forms under reaction conditions. Notably unclear is the nature of their active sites and the details of the varying oxidation states and atomic arrangements of the catalytic components during chemical reactions. In this work, we describe multimodal methods that provide a quantitative characterization of the complex heterogeneity present in the chemical and electronic speciations of Pt–Ni bimetallic catalysts supported on mesoporous silica during the reverse water gas shift reaction. The analytical protocols involved a correlated use of in situ X-ray Absorption Spectroscopy (XAS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), complimented by ex-situ aberration corrected Scanning Transmission Electron Microscopy (STEM). The data reveal that complex reactions occur between the metals and support in this system under operando conditions. These reactions, and the specific impacts of strong metal–silica bonding interactions, prevent the formation of alloy phases containing Ni–Ni bonds. This feature of structure provides high activity and selectivity for the reduction of CO2 to carbon monoxide without significant competitive levels ofmore » methanation. In conclusion, we show how these chemistries evolve to the active state of the catalyst: bimetallic nanoparticles possessing an intermetallic structure (the active phase) that are conjoined with Ni-rich, metal-silicate species.« less

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [3];  [4]; ORCiD logo [5];  [5];  [5]; ORCiD logo [6]; ORCiD logo [7];  [1]; ORCiD logo [8]
+ Show Author Affiliations
  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry
  2. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry; Columbia Univ., New York, NY (United States). Dept. of Chemical Enginerring
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering
  8. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1466591
Report Number(s):
BNL-207996-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 5; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bimetallic nanoparticles; catalysis; DRIFTS; nickel; platinum; reverse water gas shift; STEM; XAS

Citation Formats

Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., and Frenkel, Anatoly I. Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b00706.
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Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., & Frenkel, Anatoly I. Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches. United States. https://doi.org/10.1021/acscatal.8b00706
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Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., and Frenkel, Anatoly I. Mon . "Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches". United States. https://doi.org/10.1021/acscatal.8b00706. https://www.osti.gov/servlets/purl/1466591.
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@article{osti_1466591,
title = {Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches},
author = {Liu, Deyu and Li, Yuanyuan and Kottwitz, Matthew and Yan, Binhang and Yao, Siyu and Gamalski, Andrew and Grolimund, Daniel and Safonova, Olga V. and Nachtegaal, Maarten and Chen, Jingguang G. and Stach, Eric A. and Nuzzo, Ralph G. and Frenkel, Anatoly I.},
abstractNote = {Alloy nanoparticle catalysts are known to afford unique activities that can differ markedly from their parent metals, but there remains a generally limited understanding of the nature of their atomic (and likely dynamic) structures as exist in heterogeneously supported forms under reaction conditions. Notably unclear is the nature of their active sites and the details of the varying oxidation states and atomic arrangements of the catalytic components during chemical reactions. In this work, we describe multimodal methods that provide a quantitative characterization of the complex heterogeneity present in the chemical and electronic speciations of Pt–Ni bimetallic catalysts supported on mesoporous silica during the reverse water gas shift reaction. The analytical protocols involved a correlated use of in situ X-ray Absorption Spectroscopy (XAS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), complimented by ex-situ aberration corrected Scanning Transmission Electron Microscopy (STEM). The data reveal that complex reactions occur between the metals and support in this system under operando conditions. These reactions, and the specific impacts of strong metal–silica bonding interactions, prevent the formation of alloy phases containing Ni–Ni bonds. This feature of structure provides high activity and selectivity for the reduction of CO2 to carbon monoxide without significant competitive levels of methanation. In conclusion, we show how these chemistries evolve to the active state of the catalyst: bimetallic nanoparticles possessing an intermetallic structure (the active phase) that are conjoined with Ni-rich, metal-silicate species.},
doi = {10.1021/acscatal.8b00706},
journal = {ACS Catalysis},
number = 5,
volume = 8,
place = {United States},
year = {Mon Apr 02 00:00:00 EDT 2018},
month = {Mon Apr 02 00:00:00 EDT 2018}
}
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https://doi.org/10.1021/acscatal.8b00706
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Works referenced in this record:

Catalysis by alloys and bimetallic clusters
journal, January 1977

Bimetallic catalysts for upgrading of biomass to fuels and chemicals
journal, January 2012

  • Alonso, David Martin; Wettstein, Stephanie G.; Dumesic, James A.
  • Chemical Society Reviews, Vol. 41, Issue 24, p. 8075-8098
  • DOI: 10.1039/c2cs35188a

Glycerol hydrogenolysis on carbon-supported PtRu and AuRu bimetallic catalysts
journal, October 2007

Designing bimetallic catalysts for a green and sustainable future
journal, January 2012

  • Sankar, Meenakshisundaram; Dimitratos, Nikolaos; Miedziak, Peter J.
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35296f

Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction
journal, April 2010

  • Hansgen, Danielle A.; Vlachos, Dionisios G.; Chen, Jingguang G.
  • Nature Chemistry, Vol. 2, Issue 6
  • DOI: 10.1038/nchem.626

Catalyst Design by Interpolation in the Periodic Table:  Bimetallic Ammonia Synthesis Catalysts
journal, August 2001

  • Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S.
  • Journal of the American Chemical Society, Vol. 123, Issue 34
  • DOI: 10.1021/ja010963d

A Series of NiM (M = Ru, Rh, and Pd) Bimetallic Catalysts for Effective Lignin Hydrogenolysis in Water
journal, April 2014

  • Zhang, Jiaguang; Teo, Jason; Chen, Xi
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs401199f

Strong Interactions in Supported-Metal Catalysts
journal, March 1981

Methane steam reforming, methanation and water-gas shift: I. Intrinsic kinetics
journal, January 1989

Low-temperature water-gas shift reaction over Cu- and Ni-loaded cerium oxide catalysts
journal, August 2000

Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO 2 Catalyst
journal, December 2004

  • Goguet, Alexandre; Meunier, Frederic C.; Tibiletti, Daniele
  • The Journal of Physical Chemistry B, Vol. 108, Issue 52
  • DOI: 10.1021/jp047242w

Advances in the Development of Novel Cobalt Fischer−Tropsch Catalysts for Synthesis of Long-Chain Hydrocarbons and Clean Fuels
journal, May 2007

  • Khodakov, Andrei Y.; Chu, Wei; Fongarland, Pascal
  • Chemical Reviews, Vol. 107, Issue 5
  • DOI: 10.1021/cr050972v

Hydrogenation of carbon dioxide on group viii metals
journal, August 1983

Hydrogenation of CO2 on group VIII metals II. Kinetics and mechanism of CO2 hydrogenation on nickel
journal, October 1982

Surface chemistry of carbon dioxide
journal, January 1996

Insights into the mechanisms of CO2 methanation on Ni(111) surfaces by density functional theory
journal, October 2015

WGS Catalysis and In Situ Studies of CoO 1– x , PtCo n /Co 3 O 4 , and Pt m Co m ′ /CoO 1– x Nanorod Catalysts
journal, May 2013

  • Zhang, Shiran; Shan, Jun-jun; Zhu, Yuan
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja401967y

Structural changes of Au–Cu bimetallic catalysts in CO oxidation: In situ XRD, EPR, XANES, and FT-IR characterizations
journal, March 2011

Applications of extended X-ray absorption fine-structure spectroscopy to studies of bimetallic nanoparticle catalysts
journal, January 2012

Revealing the Atomic Restructuring of Pt–Co Nanoparticles
journal, May 2014

  • Xin, Huolin L.; Alayoglu, Selim; Tao, Runzhe
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl500553a

Reversible surface structural changes in Pt-based bimetallic nanoparticles during oxidation and reduction cycles
journal, May 2009

Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
journal, March 2002

Dynamic in situ observation of rapid size and shape change of supported Pd nanoparticles during CO/NO cycling
journal, May 2007

  • Newton, Mark A.; Belver-Coldeira, Carolina; Martínez-Arias, Arturo
  • Nature Materials, Vol. 6, Issue 7
  • DOI: 10.1038/nmat1924

General trend for adsorbate-induced segregation of subsurface metal atoms in bimetallic surfaces
journal, May 2009

  • Menning, Carl A.; Chen, Jingguang G.
  • The Journal of Chemical Physics, Vol. 130, Issue 17
  • DOI: 10.1063/1.3125926

Challenges and opportunities in correlating bimetallic model surfaces and supported catalysts
journal, December 2013

Oscillation of Surface Structure and Reactivity of PtNi Bimetallic Catalysts with Redox Treatments at Variable Temperatures
journal, October 2011

  • Mu, Rentao; Guo, Xiaoguang; Fu, Qiang
  • The Journal of Physical Chemistry C, Vol. 115, Issue 42
  • DOI: 10.1021/jp206517r

Complex structural dynamics of nanocatalysts revealed in Operando conditions by correlated imaging and spectroscopy probes
journal, June 2015

  • Li, Y.; Zakharov, D.; Zhao, S.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8583

Operando Characterization of Catalysts through use of a Portable Microreactor
journal, October 2015

In situ diffuse reflectance IR spectroscopy and X-ray absorption spectroscopy for fast catalytic processes
journal, April 2011

  • Marinkovic, Nebojsa S.; Wang, Qi; Frenkel, Anatoly I.
  • Journal of Synchrotron Radiation, Vol. 18, Issue 3
  • DOI: 10.1107/S0909049511005802

Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012

  • Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
  • DOI: 10.1021/cr300096b

Correlating extent of Pt–Ni bond formation with low-temperature hydrogenation of benzene and 1,3-butadiene over supported Pt/Ni bimetallic catalysts
journal, May 2010

  • Lonergan, William W.; Vlachos, Dionisios G.; Chen, Jingguang G.
  • Journal of Catalysis, Vol. 271, Issue 2
  • DOI: 10.1016/j.jcat.2010.01.019

CO methanation over supported bimetallic Ni–Fe catalysts: From computational studies towards catalyst optimization
journal, March 2007

Effect of the bimetallic Ni/Cu loading on the ZrO2 support for H2 production in the autothermal steam reforming of methanol
journal, July 2015

Correlating Ethylene Glycol Reforming Activity with In Situ EXAFS Detection of Ni Segregation in Supported NiPt Bimetallic Catalysts
journal, September 2012

  • Tupy, Sarah A.; Karim, Ayman M.; Bagia, Christina
  • ACS Catalysis, Vol. 2, Issue 11
  • DOI: 10.1021/cs3004227

Synthesis and electrocatalytic oxygen reduction properties of truncated octahedral Pt3Ni nanoparticles
journal, October 2010

Preparation of highly dispersed catalytic metals Platinum supported on silica gel
journal, April 1968

In Situ Synthesis of Noble Metal Nanoparticles in Ultrathin TiO 2 −Gel Films by a Combination of Ion-Exchange and Reduction Processes
journal, November 2002

  • He, Junhui; Ichinose, Izumi; Kunitake, Toyoki
  • Langmuir, Vol. 18, Issue 25
  • DOI: 10.1021/la0260584

Highly Dispersed Metal Nanoparticles in Functionalized SBA-15
journal, January 2003

  • Yang, Chia-min; Liu, Pang-hung; Ho, You-fu
  • Chemistry of Materials, Vol. 15, Issue 1
  • DOI: 10.1021/cm020822q

Preparation, characterization and activities of the nano-sized Ni/SBA-15 catalyst for producing COx-free hydrogen from ammonia
journal, March 2008

Trends in the catalytic reduction of CO2 by hydrogen over supported monometallic and bimetallic catalysts
journal, May 2013

CO2 Hydrogenation Studies on Co and CoPt Bimetallic Nanoparticles Under Reaction Conditions Using TEM, XPS and NEXAFS
journal, August 2011

A Novel γ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction
journal, September 2013

  • Kharaji, Abolfazl Gharibi; Shariati, Ahmad; Takassi, Mohammad Ali
  • Chinese Journal of Chemical Engineering, Vol. 21, Issue 9
  • DOI: 10.1016/S1004-9541(13)60573-X

Infrared study of effects of sulphur-poisoning on the adsorption of carbon monoxide by nickel
journal, January 1977

  • Rochester, Colin H.; Terrell, Robert J.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0
  • DOI: 10.1039/f19777300609

Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation
journal, February 2011

  • Mu, Rentao; Fu, Qiang; Xu, Hong
  • Journal of the American Chemical Society, Vol. 133, Issue 6
  • DOI: 10.1021/ja109483a

Asymmetric pathways in the electrochemical conversion reaction of NiO as battery electrode with high storage capacity
journal, November 2014

  • Boesenberg, Ulrike; Marcus, Matthew A.; Shukla, Alpesh K.
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep07133

Molecular Approach to the Mechanism of Deposition−Precipitation of the Ni(II) Phase on Silica
journal, April 1998

  • Burattin, Paolo; Che, Michel; Louis, Catherine
  • The Journal of Physical Chemistry B, Vol. 102, Issue 15
  • DOI: 10.1021/jp980018k

Metal Particle Size in Ni/SiO 2 Materials Prepared by Deposition−Precipitation:  Influence of the Nature of the Ni(II) Phase and of Its Interaction with the Support
journal, July 1999

  • Burattin, Paolo; Che, Michel; Louis, Catherine
  • The Journal of Physical Chemistry B, Vol. 103, Issue 30
  • DOI: 10.1021/jp990115t

Characterization and catalytic activity of Ni/SBA-15, synthesized by deposition–precipitation
journal, October 2005

Influence of the cobalt salt precursors on the cobalt speciation and catalytic properties of H-ZSM-5 modified with cobalt by solid-state ion exchange reaction
journal, March 2009

  • Mhamdi, Mourad; Khaddar-Zine, Sihem; Ghorbel, Abdelhamid
  • Applied Catalysis A: General, Vol. 357, Issue 1
  • DOI: 10.1016/j.apcata.2008.12.036

Bimetallic Nanocrystals: Liquid-Phase Synthesis and Catalytic Applications
journal, January 2011

Nucleation and Particle Growth Processes Involved in the Preparation of Silica-Supported Nickel Materials by a Two-Step Procedure
journal, February 1995

  • Che, Michel; Cheng, Zheng Xing; Louis, Catherine
  • Journal of the American Chemical Society, Vol. 117, Issue 7
  • DOI: 10.1021/ja00112a014

Solving the 3D structure of metal nanoparticles
journal, January 2007

Geometrical Characteristics of Regular Polyhedra: Application to EXAFS Studies of Nanoclusters
conference, January 2007

  • Glasner, Dana; Frenkel, Anatoly I.
  • X-RAY ABSORPTION FINE STRUCTURE - XAFS13: 13th International Conference, AIP Conference Proceedings
  • DOI: 10.1063/1.2644651

Determination of Nanoparticle Size by Measuring the Metal–Metal Bond Length: The Case of Palladium Hydride
journal, December 2014

  • Wang, Jianqiang; Wang, Qi; Jiang, Xinghua
  • The Journal of Physical Chemistry C, Vol. 119, Issue 1
  • DOI: 10.1021/jp510730a

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene
journal, August 2017

  • Zhao, Shen; Li, Yuanyuan; Liu, Deyu
  • The Journal of Physical Chemistry C, Vol. 121, Issue 34
  • DOI: 10.1021/acs.jpcc.7b06270

Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011

  • Wang, Wei; Wang, Shengping; Ma, Xinbin
  • Chemical Society Reviews, Vol. 40, Issue 7
  • DOI: 10.1039/c1cs15008a

Methanation of carbon dioxide: an overview
journal, December 2010

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    journal, August 2018

    • Filez, Matthias; Poelman, Hilde; Redekop, Evgeniy A.
    • Angewandte Chemie International Edition, Vol. 57, Issue 38
    • DOI: 10.1002/anie.201806447

    Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity
    journal, November 2019

    • van Deelen, Tom W.; Hernández Mejía, Carlos; de Jong, Krijn P.
    • Nature Catalysis, Vol. 2, Issue 11
    • DOI: 10.1038/s41929-019-0364-x

    Selective steam reforming of n ‐dodecane over stable subnanometric NiPt clusters encapsulated in Silicalite‐1 zeolite
    journal, January 2020

    • Zhang, Bofeng; Tian, Yajie; Chen, Dali
    • AIChE Journal, Vol. 66, Issue 5
    • DOI: 10.1002/aic.16917

    Porous hypercrosslinked polymer-TiO2-graphene composite photocatalysts for visible-light-driven CO2 conversion
    journal, February 2019

    Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X-ray Absorption Spectroscopy
    journal, August 2018

    • Filez, Matthias; Poelman, Hilde; Redekop, Evgeniy A.
    • Angewandte Chemie, Vol. 130, Issue 38
    • DOI: 10.1002/ange.201806447

    Infrared spectroscopy data- and physics-driven machine learning for characterizing surface microstructure of complex materials
    journal, March 2020

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