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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]
+ Show Author Affiliations
  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.
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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. https://doi.org/10.1039/C8SC01956H
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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. https://doi.org/10.1039/C8SC01956H.
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@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}
}
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Journal Article:
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https://doi.org/10.1039/C8SC01956H
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Cited by: 20 works
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Figures / Tables:

Fig. 1 Fig. 1: Schematic representation of the experimental approach: (a) OH-functionalized NHCs (marked with orange pentagons) were anchored to the surfaces of Pt particles (grey circles). The particles were supported on a SiO2/Si(110) wafer. Under oxidizing conditions the catalytically active Pt particles oxidize the hydroxyl group of the anchored NHCs. (b)more » High spatial resolution Synchrotron Infrared Nanospectroscopy (SINS) measurements were performed to identify site-dependent reactivity on single particles. In this setup, an AFM tip acts as an optical antenna by localizing the diffraction-limited IR beam (which has a focal spot of about 10 μm) and inducing an IR scattering signal with a tip-limited spot size of ~20 nm. (c) Chemical and structural characterization of surface-anchored NHCs was achieved by conducting ensemble-based Near Edge X-ray Absorption Fine Structure (NEXAFS), X-ray photoelectron spectroscopy (XPS) and Infrared Reflection Absorption Spectroscopy (IRRAS) measurements.« less
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    Works referencing / citing this record:

    Flexible NO 2 ‐Functionalized N‐Heterocyclic Carbene Monolayers on Au(111) Surface
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    • Dery, Shahar; Kim, Suhong; Tomaschun, Gabriele
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    Generation and conversion of an N-heterocyclic carbene on Pt(111)
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    • Chemical Communications, Vol. 54, Issue 88
    • DOI: 10.1039/c8cc06894a
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