Reaction Specificity of Nanoparticles in Solution (PNNL Scope # 42184/44076, Baer/Amonette Nano-Fe BES/EMSP project)
EMSL Project ID
2573a
Abstract
This User Proposal is being submitted as part of an approved NSET proposal under PIs Don Baer and Paul Tratnyek to perform fundamental basic science studies that will benefit a whole range of applications involving nanoparticles in solution, including environmental remediation, corrosion, magnetic-storage media, and heterogeneous catalysis. The following is an excerpt from the abstract of the NSET proposal. The reactivity of nanometer-sized materials is often quite different from that of either the bulk material or the individual atoms and molecules that comprise it. Much of this size-dependent reactivity stems from the development of unique electronic structures intermediate between those of bulk materials and free atoms. Zero-valent iron (Fe) represents one system whose chemistry exhibits intrinsic nanoscale reactivity as well as the transition from metallic to semiconducting behavior. Iron and iron bimetallic nanoparticles have been shown to have a greatly increased reactivity towards a variety of environmentally important solute species including chlorinated hydrocarbons and reducible oxyanions. Furthermore, the products of these reactions differ, often in an environmentally friendly manner, from those obtained when 0.1 to 1mm particles of Fe are used. These changes occur for particles of the size range where signficant variations in electronic and magnetic properties are induced for pure metal particles. However, the Fe particles will have the additional complication of a reaction layer that forms on the surface in solution. The differences in selectivity are believed to be related to unique structural and chemical features of Fe(0) near the solution and/or Fe(II) in the oxide coating. The differences may be induced by the changes in the electronic structure of the nano-sized particles or changes in the structure of the coatings formed on the particles in solution. In order to establish and quantify these effects, this proposal defines a coupled experimental and modeling research program for studying reactive metal, bimetallic, and oxide nanoparticles, using chlorinated hydroarbons and inorganic oxyanions as model compounds...Novel and established techniques will be used for preparing iron and iron bimetallic nanoparicles in both the solution and gas phases. These particles and their surfaces will be subjected to advanced characterizaiton studies that will include magnetic measurements, high resolution transmission electron microscopy (HRTEM), scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), electron paramagenetic resonance (EPR) and other methods.
Project Details
Project type
Exploratory Research
Start Date
2005-10-04
End Date
2006-11-10
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
6: Jiji Antony, Joseph Nutting, D. Baer, Daniel Meyer, Amit Sharma, and You Qiang, “Size dependent specific surface area of nanoporous films assembled by core-shell iron nanoclusters”, J. of Nanomaterials, 12 (2006) 54961.
Baer DR, and MH Engelhard. 2010. "XPS Analysis of Nanostructured Materials and Biological Surfaces." Journal of Electron Spectroscopy and Related Phenomena 178-179:415-432. doi:10.1016/j.elspec.2009.09.003
Baer DR, MH Engelhard, C Wang, AS Lea, and KH Pecher. 2006. “The Challenges and Opportunities of Measuring Properties of Nanoparticles and Nanostructured Materials: Importance of a Multi-Technique Approach.” 2006 TAPPI International Conference on Nanotechnology for the Forest Products Industry. Paper 06NANO20 http://www.tappi.org/index.asp?rc=1&pid=34455&ch=8&bhcd2=1146525637.
Baer DR, PG Tratnyek, Y Qiang, JE Amonette, JC Linehan, V Sarathy, JT Nurmi, CM Wang, and J Antony. 2007. "Synthesis, Characterization and Properties of Zero Valent Iron Nanoparticles." In “Environmental Applications of Nanomaterials: Synthesis, Sorbents, and Sensors” edited by Dr. Glen Fryxell (PNNL) and Professor Guozhong Cao University of Washington Imperial College Press
Baer, DR. “Sharpening our Understanding but Blurring the Boundaries: Dynamic Observations of Surface Reconstruction.” Surface Science 540 (2003)153-156.
Bluhm, H, K Andersson, T Araki, K Benzerara, GE Brown, JJ Dynes, S Ghosal, MK Gilles, H-Ch Hansen, JC Hemminger, AP Hitchcock, G Ketteler, ALD Kilcoyne, E Kneedler, JR Lawrence, GG Leppard, J Majzlam, BS Mun, SCB Myneni, A Nilsson, H Ogasawara, DF Ogletree, K Pecher, M Salmeron, DK Shuh, B Tonner, T Tyliszczak, T Warwick, TH Yoon. “Soft X-ray Microscopy and Spectroscopy at the Molecular Environmental Science Beamline at the Advanced Light Source”, Journal of Electron Spectroscopy and Related Phenomena, 150 (2-3) (2006) 86-104.
Bylaska EJ “Estimating the Thermodynamics and Kinetics of Chlorinated Hydrocarbon Degradation”, Theoretical Chemistry Accounts, 116 (1-3): 281-296 (2006).
Bylaska, EJ., M Dupuis, and PG Tratnyek. "One-Electron Reduction of Polychlorinated Ethylenes as Determined from Ab Initio Electronic Structure Theory.", J. Phys Chem A. 109 (2005) 5905-5916.
Daschbach, JL, Z Dohnálek, S Liu, RS Smith, and BD Kay, “Water Adsorption, Desorption and Clustering on FeO(111).”, Journal of Physical Chemistry B 109 (2005) 10362-10370.
Dohnálek Z, J. Kim, and B. D. Kay, “Growth of Epitaxial Thin Pd(111) Films on Pt(111) and Oxygen Terminated FeO(111) Surfaces.”, Surface Science 600 (2006) 3461.
Gaspar, DJ, AS Lea, MH Engelhard, DR Baer, R Miehr, and PG Tratnyek. “Evidence for Localization of Reaction Upon Reduction of Carbon Tetrachloride by Granular Iron.” Langmuir 18 (2002) 7688-7693.
Liu, S, Z Dohnálek, RS Smith, and BD Kay, “Interaction of CH4, CH3Cl, CH2Cl2, CHCl3, and CCl4 with O-terminated FeO (111)” Surface, Journal of Physical Chemistry B, 108 (2004) 3644.
Meyer DR, M Faheem, M Campanell, J Antony, AM Sharma, and Y Qiang. 2007. "Magnetic Nanocrystalline Films Softened by Obliquely Accelerating Iron Nanoclusters." IEEE Transactions on Magnetics 43(6):3010-3012. doi:10.1109/TMAG.2007.893477
Qiang Y, J Antony, A Sharma, J Nutting, D Sikes and D Meyer, “Iron/iron Oxide Core-Shell Nanoclusters for Biomedical Applications”, J. of Nanoparticle Research, (2006) 8: 489-496
Saraf, L, CM Wang, V Shutthanandan, Y Zhang, O Marina, DR Baer and S Thevuthasan, P Nachimuthu and DW Lindle. "Oxygen Transport Studies in Nanocrystalline Ceria Films." Journal of Materials Research 20,(2005) pp. 1295 – 1299.
Saraf, L, C Wang, MH Engelhard and DR Baer. "Temperature and Interfacial Stress Induced Phase Separation in Chromium Films." Applied Physics Letters 82 (2003) 2230-32.
Sharma A, Y Qiang, DR Meyer, R Souza, A Mcconnaughoy, L Muldoon, and DR Baer. 2008. "Biocompatible core-shell magnetic nanoparticles for cancer treatment." Journal of Applied Physics 103(7):Art. No.07A308. doi:10.1063/1.2831791
Wang, CM, DR Baer, J. Amonette, MH Engelhard, Y Qiang, and J Antony, (2007). “Morphology and Oxide Shell Structure of Iron Nanoparticles Grown by Sputter-Gas-Aggregation” Nanotechnology 18: 255603
Wang CM, DR Baer, JE Amonette, MH Engelhard, JS Anthony, and Y Qiang. (2007). "Electron Beam Induced Thickening of the Protective Oxide Layer around Fe Nanoparticles.” Ultramicroscopy doi:10.1016/j.ultramic.2007.03.002