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Molecular-scale visualization of ligand conformation on functionalized nanoparticles: A combination of experimental and theoretical studies

EMSL Project ID


The goal of this project is to develop capabilities that will advance the fundamental understanding of the interaction between the nanoparticles surfaces and organic ligand molecules as applicable to dye-sensitized solar cells, contamination remediation in the ground water and drug delivery in the biological systems. This would be accomplished by using CeO2 nanoparticles and organic ligands with carboxylate and phosphonate functional groups, applying existing and newly developed tools at EMSL to characterize the nanoparticle-ligand interactions and by measuring the impact of the derivatives on the organic ligands, the variation of the surface potential of the nanoparticles surfaces and their particle sizes. The results on these systems will provide information about the structural and electronic aspects at molecular level, the chemical state of elements in the nanoparticle and organic coating, number of ligand molecules on the particle surface, their orientation and nature of packing. Mainly, the non-linear optical methods, sum frequency generation-vibrational spectroscopy (SFG-VS) and the second harmonic generation (SHG) will be used to characterize the functional groups and their conformation on the nanoparticle surfaces (the bonding sites, bond strength, and bond directions of ligand molecules on ceria nanoparticles) in addition to x-ray photoelectron spectroscopy, UV-Vis spectroscopy, and electron microscopy for physical and electronic structure information. First principle calculations will provide critical insights into the surface structure, the conformation of binding ligands, and the chemical nature of bonding interactions. The combined and complementary data sets from theoretical studies and experimental efforts will help us visualize and elucidate the, often complicated, nature of cerium oxide nanoparticle-ligand systems and help extend the understanding to other relevant systems in future. These efforts combining experimental measurements and theoretical studies to comprehensively understand the functionalized nanoparticles will enable a team poised to help address the issues of fundamental and applied interest in the area of nanoparticles’ research.

Project Details

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Principal Investigator

Theva Thevuthasan
Environmental Molecular Sciences Laboratory

Team Members

Weina Wang
Shaanxi Normal University

Hongfei Wang
Fudan University

Ping Yang
Los Alamos National Laboratory

Ajay Karakoti
Pacific Northwest National Laboratory

Satyanarayana Kuchibhatla
Battelle India

Ponnusamy Nachimuthu
Environmental Molecular Sciences Laboratory

Sudipta Seal
University of Central Florida

Chongmin Wang
Environmental Molecular Sciences Laboratory

Related Publications

Baer DR, MH Engelhard, GE Johnson, J Laskin, J Lai, KT Mueller, P Munusamy, S Thevuthasan, H Wang, NM Washton, AC Elder, BL Baisch, AS Karakoti, SVNT Kuchibhatla, and DW Moon. 2013. "Surface Characterization of Nanomaterials and Nanoparticles: important needs and challenging opportunities." Journal of Vacuum Science and Technology A--Vacuum, Surfaces and Films 31(5):Article No. 050820. doi:10.1116/1.4818423.
Bhagat S, NS Vallabani, V Shutthanandan, ME Bowden, AS Karakoti, and S Singh. 2018. "Gold Core/Ceria Shell-Based Redox Active Nanozyme Mimicking the Biological Multienzyme Complex Phenomenon." Journal of Colloid and Interface Science 513:831-842. doi:10.1016/j.jcis.2017.11.064
Gao Y, B Zhou, S-G Kang, M Xin, P Yang, X Dai, Z Wang, and R Zhou. 2014. "Effect of ligands on the characteristics of (CdSe)13 quantum dots." RSC Advances 4:27146-27151. doi:10.1039/C4RA03202K
Kang S, G Zhou, P Yang, Y Liu, B Sun, T Huynh, H Meng, L Zhao, G Xing, C Chen, Y Zhao, and R Zhou. 2012. "Molecular Mechanism of Pancreatic Tumor Metastasis Inhibition by Gd@C?? (OH)?? and its Implication for de novo Design of Nanomedicine." Proceedings of the National Academy of Sciences of the United States of America 109(38):15431-15436. doi:10.1073/pnas.1204600109
Karakoti AS, P Yang, W Wang, V Patel, AI Martinez, V Shutthanandan, S Seal, and S Thevuthasan. 2018. "Investigation of the Ligand-Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry." Journal of Physical Chemistry C 122(6):3582-3590. doi:10.1021/acs.jpcc.7b09930
Kuchibhatla SVNT, AS Karakoti, S Thevuthasan, S Seal, and DR Baer. 2012. "Influence of Aging on the Properties of Cerium Oxide Nanoparticles Implications to Quantum Confinement Effect." In 11th IEEE conference on Nanotchenology 2011, pp. 646-650. IEEE Robotics & Automation Society; Institute of Electrical & Electronics Engineers, Piscataway, NJ. doi:10.1109/NANO.2011.6144639
Lu Z, AS Karakoti, LA Velarde Ruiz Esparza, W Wang, P Yang, S Thevuthasan, and H Wang. 2013. "Dissociative Binding of Carboxylic Acid Ligand on Nanoceria Surface in Aqueous Solution: A Joint in Situ Spectroscopic Characterization and First-Principles Study." Journal of Physical Chemistry C 117(46):24329-24338. doi:10.1021/jp4068747
Munusamy P, SP Sanghavi, T Varga, and S Thevuthasan. 2014. "Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria." RSC Advances 4(17):8421-8430. doi:10.1039/c3ra44345k
Sanghavi SP, AS Karakoti, MI Nandasiri, W Wang, P Nachimuthu, P Yang, and S Thevuthasan. 2016. "Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces." Journal of Physical Chemistry C 2016:1-7. doi:10. 1039/c6cp00855k
Wang W, S Thevuthasan, W Wang, P Yang, and ME Bowden. 2016. "Theoretical Study of Trimethylacetic Acid Adsorption on CeO2(111) Surface." PNNL-SA-117246, Pacific Northwest National Laboratory, Richland, WA. [Unpublished]
Yang P, S Tretiak, and S Ivanov. 2011. "Influence of Surfactants and Charges on CdSe Quantum Dots." Journal of Cluster Science 22(3):405-431. doi:10.1007/s10876-011-0398-y
Zhou Y, P Yang, X Sun, Z Wang, XT Zu, and F Gao. 2011. "First-principles study of the noble metal-doped BN layer." Journal of Applied Physics 109(8):Article No. 084308. doi:10.1063/1.3569725
Zhou Y, P Yang, Z Wang, HY Xiao, XT Zu, X Sun, MA Khaleel, and F Gao. 2011. "Functionalized Graphene Nanoroads for Quantum Well Device." Applied Physics Letters 98(9):093108. doi:10.1063/1.3560981