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Title: Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry

Abstract

Ligand functionalized nanoparticles have replaced bare nanoparticles from most biological applications. These applications require tight control over size and stability of nanoparticles in aqueous medium. Understanding the mechanism of interaction of nanoparticle surfaces with functional groups of different organic ligands such as carboxylic acids is confounding despite the two decades of research on nanoparticles because of the inability to characterize their surfaces in their immediate environment. Often the surface interaction is understood by correlating the information available, in a piecemeal approach, from surface sensitive spectroscopic information of ligands and the bulk and surface information of nanoparticles. In present study we report the direct interaction of 5-7 nm cerium oxide nanoparticles surface with acetic acid. In-situ XPS study was carried out by freezing the aqueous solution of nanoparticles to liquid nitrogen temperatures. Analysis of data collected concurrently from the ligands as well as functionalized frozen cerium oxide nanoparticles show that the acetic acid binds to the ceria surface in both dissociated and molecular state with equal population over the surface. The cerium oxide surface was populated predominantly with Ce4+ ions consistent with the thermal hydrolysis synthesis. DFT calculations reveal that the acetate ions bind more strongly to the cerium oxide nanoparticlesmore » as compared to the water and can replace the hydration sphere of nanoparticles resulting in high acetate/acetic surface coverage. These findings reveal molecular level interaction between the nanoparticle surfaces and ligands giving a better understanding of how materials behave in their immediate aqueous environment. This study also proposes a simple and elegant methodology to directly study the surface functional groups attached to nanoparticles in their immediate aqueous environment.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [5];  [5];  [6];  [5]
  1. School of Engineering and Applied Science, Ahmedabad University, Ahmedabad, Gujarat 380009, India; Division of Biological and Life Sciences, School of Arts and Sciences, Ahmedabad University, Ahmedabad, Gujarat 380009 India
  2. Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
  3. School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi China 710062
  4. Division of Biological and Life Sciences, School of Arts and Sciences, Ahmedabad University, Ahmedabad, Gujarat 380009 India
  5. EMSL, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  6. Nanoscience and Technology Centre, University of Central Florida, Orlando, Florida 32826, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1438993
Report Number(s):
PNNL-SA-131439
Journal ID: ISSN 1932-7447; 39891; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 122; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Karakoti, Ajay S., Yang, Ping, Wang, Weina, Patel, Vaishwik, Martinez, Abraham, Shutthanandan, Vaithiyalingam, Seal, Sudipta, and Thevuthasan, Suntharampillai. Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b09930.
Karakoti, Ajay S., Yang, Ping, Wang, Weina, Patel, Vaishwik, Martinez, Abraham, Shutthanandan, Vaithiyalingam, Seal, Sudipta, & Thevuthasan, Suntharampillai. Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry. United States. doi:10.1021/acs.jpcc.7b09930.
Karakoti, Ajay S., Yang, Ping, Wang, Weina, Patel, Vaishwik, Martinez, Abraham, Shutthanandan, Vaithiyalingam, Seal, Sudipta, and Thevuthasan, Suntharampillai. Fri . "Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry". United States. doi:10.1021/acs.jpcc.7b09930.
@article{osti_1438993,
title = {Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry},
author = {Karakoti, Ajay S. and Yang, Ping and Wang, Weina and Patel, Vaishwik and Martinez, Abraham and Shutthanandan, Vaithiyalingam and Seal, Sudipta and Thevuthasan, Suntharampillai},
abstractNote = {Ligand functionalized nanoparticles have replaced bare nanoparticles from most biological applications. These applications require tight control over size and stability of nanoparticles in aqueous medium. Understanding the mechanism of interaction of nanoparticle surfaces with functional groups of different organic ligands such as carboxylic acids is confounding despite the two decades of research on nanoparticles because of the inability to characterize their surfaces in their immediate environment. Often the surface interaction is understood by correlating the information available, in a piecemeal approach, from surface sensitive spectroscopic information of ligands and the bulk and surface information of nanoparticles. In present study we report the direct interaction of 5-7 nm cerium oxide nanoparticles surface with acetic acid. In-situ XPS study was carried out by freezing the aqueous solution of nanoparticles to liquid nitrogen temperatures. Analysis of data collected concurrently from the ligands as well as functionalized frozen cerium oxide nanoparticles show that the acetic acid binds to the ceria surface in both dissociated and molecular state with equal population over the surface. The cerium oxide surface was populated predominantly with Ce4+ ions consistent with the thermal hydrolysis synthesis. DFT calculations reveal that the acetate ions bind more strongly to the cerium oxide nanoparticles as compared to the water and can replace the hydration sphere of nanoparticles resulting in high acetate/acetic surface coverage. These findings reveal molecular level interaction between the nanoparticle surfaces and ligands giving a better understanding of how materials behave in their immediate aqueous environment. This study also proposes a simple and elegant methodology to directly study the surface functional groups attached to nanoparticles in their immediate aqueous environment.},
doi = {10.1021/acs.jpcc.7b09930},
journal = {Journal of Physical Chemistry. C},
number = 6,
volume = 122,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2018},
month = {Fri Feb 02 00:00:00 EST 2018}
}