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Title: Identifying site-dependent reactivity in oxidation reactions on single Pt particles

Abstract

Catalytic nanoparticles are heterogeneous in their nature and even within the simplest particle various surface sites exist and influence the catalytic reactivity. Thus, detailed chemical information at the nanoscale is essential for understanding how surface properties and reaction conditions direct the reactivity of different surface sites of catalytic nanoparticles. In this work, hydroxyl-functionalized Nheterocyclic carbene molecules (NHCs) were anchored to the surface of Pt particles and utilized as chemical markers to detect reactivity variations between different surface sites under liquid and gas phase oxidizing conditions. Differences in the chemical reactivity of surface-anchored NHCs were identified using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 20 nanometers. By conducting IR nanospectroscopy measurements, along with complementary spatially averaged IR and X-ray spectroscopy measurements, we identified that enhanced reactivity occurred on the particles' periphery under both gas and liquid phase oxidizing conditions. Under gas phase reaction conditions the NHCs' hydroxyl functional groups underwent preferential oxidization to the acid along the perimeter of the particle. Exposure of the sample to harsher, liquid phase oxidizing conditions induced modification of the NHCs, which was mostly identified at the particle's periphery. Analysis of X-ray absorption spectroscopy measurements revealed that exposure of the sample to oxidizing conditions inducedmore » aromatization of the NHCs, presumably due to oxidative dehydrogenation reaction, along with reorientation of the NHCs from perpendicular to parallel to the Pt surface. These results, based on single particle measurements, demonstrate the high reactivity of surface sites that are located at the nanoparticle's periphery and the influence of reaction conditions on site-dependent reactivity.« less

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, The Center for Nanoscience and Nanotechnology
  2. Department of Chemistry, University of California, Berkeley, USA
  3. CNR-IOM, Laboratorio Nazionale TASC, Trieste 34012, Italy
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; United States-Israel Binational Science Foundation (BSF); Ministry of Energy; Rudin Fellowship
OSTI Identifier:
1459728
Alternate Identifier(s):
OSTI ID: 1624962
Grant/Contract Number:  
AC02-05CH11231; 2016344
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 31; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Dery, Shahar, Kim, Suhong, Haddad, David, Cossaro, Albano, Verdini, Alberto, Floreano, Luca, Toste, F. Dean, and Gross, Elad. Identifying site-dependent reactivity in oxidation reactions on single Pt particles. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC01956H.
Dery, Shahar, Kim, Suhong, Haddad, David, Cossaro, Albano, Verdini, Alberto, Floreano, Luca, Toste, F. Dean, & Gross, Elad. Identifying site-dependent reactivity in oxidation reactions on single Pt particles. United Kingdom. doi:10.1039/C8SC01956H.
Dery, Shahar, Kim, Suhong, Haddad, David, Cossaro, Albano, Verdini, Alberto, Floreano, Luca, Toste, F. Dean, and Gross, Elad. Tue . "Identifying site-dependent reactivity in oxidation reactions on single Pt particles". United Kingdom. doi:10.1039/C8SC01956H.
@article{osti_1459728,
title = {Identifying site-dependent reactivity in oxidation reactions on single Pt particles},
author = {Dery, Shahar and Kim, Suhong and Haddad, David and Cossaro, Albano and Verdini, Alberto and Floreano, Luca and Toste, F. Dean and Gross, Elad},
abstractNote = {Catalytic nanoparticles are heterogeneous in their nature and even within the simplest particle various surface sites exist and influence the catalytic reactivity. Thus, detailed chemical information at the nanoscale is essential for understanding how surface properties and reaction conditions direct the reactivity of different surface sites of catalytic nanoparticles. In this work, hydroxyl-functionalized Nheterocyclic carbene molecules (NHCs) were anchored to the surface of Pt particles and utilized as chemical markers to detect reactivity variations between different surface sites under liquid and gas phase oxidizing conditions. Differences in the chemical reactivity of surface-anchored NHCs were identified using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 20 nanometers. By conducting IR nanospectroscopy measurements, along with complementary spatially averaged IR and X-ray spectroscopy measurements, we identified that enhanced reactivity occurred on the particles' periphery under both gas and liquid phase oxidizing conditions. Under gas phase reaction conditions the NHCs' hydroxyl functional groups underwent preferential oxidization to the acid along the perimeter of the particle. Exposure of the sample to harsher, liquid phase oxidizing conditions induced modification of the NHCs, which was mostly identified at the particle's periphery. Analysis of X-ray absorption spectroscopy measurements revealed that exposure of the sample to oxidizing conditions induced aromatization of the NHCs, presumably due to oxidative dehydrogenation reaction, along with reorientation of the NHCs from perpendicular to parallel to the Pt surface. These results, based on single particle measurements, demonstrate the high reactivity of surface sites that are located at the nanoparticle's periphery and the influence of reaction conditions on site-dependent reactivity.},
doi = {10.1039/C8SC01956H},
journal = {Chemical Science},
number = 31,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C8SC01956H

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Works referenced in this record:

High spatial resolution mapping of chemically-active self-assembled N-heterocyclic carbenes on Pt nanoparticles
journal, January 2016


Mechanism of catalysis of hydrocarbon reactions by platinum surfaces
journal, December 1975

  • Somorjai, G. A.; Blakely, D. W.
  • Nature, Vol. 258, Issue 5536
  • DOI: 10.1038/258580a0

Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture)
journal, April 2008


XPS of nitrogen-containing functional groups on activated carbon
journal, January 1995


Direct observation of narrow mid-infrared plasmon linewidths of single metal oxide nanocrystals
journal, May 2016

  • Johns, Robert W.; Bechtel, Hans A.; Runnerstrom, Evan L.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11583

Transition-metal nanoparticles: synthesis, stability and the leaching issue
journal, January 2008

  • Pachón, Laura Durán; Rothenberg, Gadi
  • Applied Organometallic Chemistry, Vol. 22, Issue 6
  • DOI: 10.1002/aoc.1382

Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012

  • Buurmans, Inge L. C.; Weckhuysen, Bert M.
  • Nature Chemistry, Vol. 4, Issue 11
  • DOI: 10.1038/nchem.1478

Single Molecule Nanospectroscopy Visualizes Proton-Transfer Processes within a Zeolite Crystal
journal, October 2016

  • Ristanović, Zoran; Kubarev, Alexey V.; Hofkens, Johan
  • Journal of the American Chemical Society, Vol. 138, Issue 41
  • DOI: 10.1021/jacs.6b06083

Infrared and Raman imaging of heterogeneous catalysts
journal, January 2010

  • Stavitski, Eli; Weckhuysen, Bert M.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00064g

N -Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu
journal, January 2017

  • Jiang, Li; Zhang, Bodong; Médard, Guillaume
  • Chemical Science, Vol. 8, Issue 12
  • DOI: 10.1039/C7SC03777E

Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy
journal, August 2012

  • van Schrojenstein Lantman, Evelien M.; Deckert-Gaudig, Tanja; Mank, Arjan J. G.
  • Nature Nanotechnology, Vol. 7, Issue 9
  • DOI: 10.1038/nnano.2012.131

Detection, Counting, and Imaging of Single Nanoparticles
journal, December 2013

  • Wang, Wei; Tao, Nongjian
  • Analytical Chemistry, Vol. 86, Issue 1
  • DOI: 10.1021/ac403890n

XPS and NEXAFS studies of aliphatic and aromatic amine species on functionalized surfaces
journal, September 2009


Periodic Arrays of Cu-Phthalocyanine Chains on Au(110)
journal, June 2008

  • Floreano, Luca; Cossaro, Albano; Gotter, Roberto
  • The Journal of Physical Chemistry C, Vol. 112, Issue 29
  • DOI: 10.1021/jp711140e

Tunable Heterogeneous Catalysis: N-Heterocyclic Carbenes as Ligands for Supported Heterogeneous Ru/K-Al 2 O 3 Catalysts To Tune Reactivity and Selectivity
journal, August 2016

  • Ernst, Johannes B.; Muratsugu, Satoshi; Wang, Fei
  • Journal of the American Chemical Society, Vol. 138, Issue 34
  • DOI: 10.1021/jacs.6b03821

Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes
journal, June 2017

  • Ernst, Johannes B.; Schwermann, Christian; Yokota, Gen-ichi
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b05112

Developments in operando studies and in situ characterization of heterogeneous catalysts
journal, May 2003


N -Heterocyclic Carbene Self-assembled Monolayers on Copper and Gold: Dramatic Effect of Wingtip Groups on Binding, Orientation and Assembly
journal, November 2017

  • Larrea, Christian R.; Baddeley, Christopher J.; Narouz, Mina R.
  • ChemPhysChem, Vol. 18, Issue 24
  • DOI: 10.1002/cphc.201701045

Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics
journal, November 2008

  • Xu, Weilin; Kong, Jason S.; Yeh, Yun-Ting E.
  • Nature Materials, Vol. 7, Issue 12
  • DOI: 10.1038/nmat2319

Model Studies in Heterogeneous Catalysis
journal, July 2010


Molecular Factors of Catalytic Selectivity
journal, November 2008

  • Somorjai, Gabor A.; Park, Jeong Y.
  • Angewandte Chemie International Edition, Vol. 47, Issue 48
  • DOI: 10.1002/anie.200803181

Dramatically Different Kinetics and Mechanism at Solid/Liquid and Solid/Gas Interfaces for Catalytic Isopropanol Oxidation over Size-Controlled Platinum Nanoparticles
journal, July 2014

  • Wang, Hailiang; Sapi, Andras; Thompson, Christopher M.
  • Journal of the American Chemical Society, Vol. 136, Issue 29
  • DOI: 10.1021/ja505641r

An overview of N-heterocyclic carbenes
journal, June 2014

  • Hopkinson, Matthew N.; Richter, Christian; Schedler, Michael
  • Nature, Vol. 510, Issue 7506, p. 485-496
  • DOI: 10.1038/nature13384

Modular Bidentate Hybrid NHC-Thioether Ligands for the Stabilization of Palladium Nanoparticles in Various Solvents
journal, April 2016

  • Rühling, Andreas; Schaepe, Kira; Rakers, Lena
  • Angewandte Chemie International Edition, Vol. 55, Issue 19
  • DOI: 10.1002/anie.201508933

Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution
journal, November 2016


Single-Molecule Chemistry with Surface- and Tip-Enhanced Raman Spectroscopy
journal, December 2016


The orientation of Langmuir–Blodgett monolayers using NEXAFS
journal, March 1988

  • Outka, D. A.; Stöhr, J.; Rabe, J. P.
  • The Journal of Chemical Physics, Vol. 88, Issue 6
  • DOI: 10.1063/1.453862

Nanoscale mapping of catalytic activity using tip-enhanced Raman spectroscopy
journal, January 2015

  • Kumar, N.; Stephanidis, B.; Zenobi, R.
  • Nanoscale, Vol. 7, Issue 16
  • DOI: 10.1039/C4NR07441F

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


Characterization of benzenethiolate self-assembled monolayer on Cu(100) by XPS and NEXAFS
journal, May 2009

  • Beccari, Marco; Kanjilal, Aloke; Betti, Maria Grazia
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 172, Issue 1-3
  • DOI: 10.1016/j.elspec.2009.03.004

NEXAFS Studies on the Soft X-ray Induced Chemical Transformation of a 4-Nitrobenzaldimine Monolayer
journal, November 2003

  • La, Young-Hye; Jung, Yu Jin; Kang, Tai-Hee
  • Langmuir, Vol. 19, Issue 23
  • DOI: 10.1021/la0355693

Ballbot-type motion of N-heterocyclic carbenes on gold surfaces
journal, October 2016

  • Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed
  • Nature Chemistry, Vol. 9, Issue 2
  • DOI: 10.1038/nchem.2622

Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold
journal, March 2014

  • Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.
  • Nature Chemistry, Vol. 6, Issue 5
  • DOI: 10.1038/nchem.1891

Addressable Carbene Anchors for Gold Surfaces
journal, May 2013

  • Zhukhovitskiy, Aleksandr V.; Mavros, Michael G.; Van Voorhis, Troy
  • Journal of the American Chemical Society, Vol. 135, Issue 20
  • DOI: 10.1021/ja401965d

High-spatial-resolution mapping of catalytic reactions on single particles
journal, January 2017

  • Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan
  • Nature, Vol. 541, Issue 7638
  • DOI: 10.1038/nature20795

Nano-FTIR Absorption Spectroscopy of Molecular Fingerprints at 20 nm Spatial Resolution
journal, July 2012

  • Huth, Florian; Govyadinov, Alexander; Amarie, Sergiu
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301159v

Ultrabroadband infrared nanospectroscopic imaging
journal, May 2014

  • Bechtel, H. A.; Muller, E. A.; Olmon, R. L.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 20
  • DOI: 10.1073/pnas.1400502111

In Situ IR and X-ray High Spatial-Resolution Microspectroscopy Measurements of Multistep Organic Transformation in Flow Microreactor Catalyzed by Au Nanoclusters
journal, February 2014

  • Gross, Elad; Shu, Xing-Zhong; Alayoglu, Selim
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja412740p

Electronic and Geometric Characterization of the l -Cysteine Paired-Row Phase on Au(110)
journal, December 2006

  • Cossaro, Albano; Terreni, Silvana; Cavalleri, Ornella
  • Langmuir, Vol. 22, Issue 26
  • DOI: 10.1021/la061833r

Imaging the chemical activity of single nanoparticles with optical microscopy
journal, January 2018


Zwitterionic dithiocarboxylates derived from N-heterocyclic carbenes: coordination to gold surfaces
journal, January 2012

  • Siemeling, Ulrich; Memczak, Henry; Bruhn, Clemens
  • Dalton Transactions, Vol. 41, Issue 10
  • DOI: 10.1039/c2dt11976e

Nanoscale infrared imaging of zeolites using photoinduced force microscopy
journal, January 2017

  • Fu, Donglong; Park, Katie; Delen, Guusje
  • Chemical Communications, Vol. 53, Issue 97
  • DOI: 10.1039/C7CC06832H

Chemisorption geometry of pyridine on platinum(111) by NEXAFS
journal, September 1985

  • Johnson, Allen L.; Muetterties, E. L.; Stohr, J.
  • The Journal of Physical Chemistry, Vol. 89, Issue 19
  • DOI: 10.1021/j100265a029