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

Dery, Shahar; Kim, Suhong; Haddad, David; Cossaro, Albano; Verdini, Alberto; Floreano, Luca; Toste, F. Dean; Gross, Elad

doi:10.1039/C8SC01956H

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

Journal Article · 02 July 2018 · Chemical Science

DOI: https://doi.org/10.1039/C8SC01956H · OSTI ID:1459728

Dery, Shahar ^[1];

^[2]; Haddad, David ^[1];

^[3];

^[2];

^[1]

Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel, The Center for Nanoscience and Nanotechnology
Department of Chemistry, University of California, Berkeley, USA
CNR-IOM, Laboratorio Nazionale TASC, Trieste 34012, Italy

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.

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1459728

Alternate ID(s):: OSTI ID: 1624962

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 31 Vol. 9; ISSN 2041-6520; ISSN CSHCBM

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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

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