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Experimental and Theoretical Studies of Reaction Pathways for the Breakdown of Chlorinated Hydrocarbon Molecules by Metal and Metal Oxide Nanoparticles(including PNNL Scope # 42184/44076, Baer/Amonette/Tratnyek Nano-Fe BES/EMSP project)


EMSL Project ID
2573b

Abstract

Metal and metal-oxide nanoparticles have been shown to have high reactivity towards a variety of chemical species, including chlorinated hydrocarbons and reducible oxyanions that frequently contaminate ground water at DOE and other government and industrial sites. In addition to rapid reaction rates, evidence suggests that these materials offer a degree of control over product-formation pathways and therefore might be engineered to produce environmentally more-favorable products. However, the fundamental science necessary to support such applications is not yet well developed.

This research effort focuses on understanding and optimizing the reduction of halogenated hydrocarbons by reactive metal and metal-oxide particles (especially nanoparticles containing Fe0). The types of halogenated hydrocarbons studied are those that frequently contaminate ground water, with a particular emphasis on carbon tetrachloride. The scope of activities includes theoretical calculations and experimental determinations of molecular-degradation pathways. The experimental work relies on synthesis of dispersed nanoparticles for solution-phase measurements and supported particles for vacuum-based reactivity measurements. Of particular interest are the roles of particle size, shape, and composition on the reaction rates and pathways in solution.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2006-08-08
End Date
2009-09-30
Status
Closed

Team

Principal Investigator

James Amonette
Institution
Pacific Northwest National Laboratory

Team Members

Maninder Kaur Tarsem Singh
Institution
University of Idaho

Juan Liu
Institution
Peking University

Hui Che
Institution
University of Idaho

Sefik Suzer
Institution
Bilkent University

Priscilla Lee
Institution
Oregon Health & Science University

Gareth Parkinson
Institution
Vienna University of Technology

Chan Lan Chun
Institution
University of Minnesota

James Nurmi
Institution
Oregon Health & Science University

Satyanarayana Kuchibhatla
Institution
Battelle India

Amit Sharma
Institution
University of Idaho

Thomas Wietsma
Institution
Environmental Molecular Sciences Laboratory

Vaishnavi Sarathy
Institution
Oregon Health & Science University

Chongmin Wang
Institution
Environmental Molecular Sciences Laboratory

Mark Engelhard
Institution
Environmental Molecular Sciences Laboratory

You Qiang
Institution
University of Idaho

JiJi Antony
Institution
University of Idaho

Hongmei Han
Institution
University of Idaho

Donald Baer
Institution
Environmental Molecular Sciences Laboratory

Zdenek Dohnalek
Institution
Pacific Northwest National Laboratory

Bruce Kay
Institution
Pacific Northwest National Laboratory

R. Penn
Institution
University of Minnesota

Anter El-azab
Institution
Purdue University

Paul Tratnyek
Institution
Oregon Health & Science University

Eric Bylaska
Institution
Pacific Northwest National Laboratory

Michel Dupuis
Institution
University at Albany, State University of New York

Dean Matson
Institution
Pacific Northwest National Laboratory

Paul Gassman
Institution
Pacific Northwest National Laboratory

Ravi Kukkadapu
Institution
Environmental Molecular Sciences Laboratory

Related Publications

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, DJ Gaspar, P Nachimuthu, SD Techane, and DG Castner. 2010. "Application of Surface Chemical Analysis Tools for Characterization of Nanoparticles." Analytical and Bioanalytical Chemistry 396(3):983-1002. doi: 10.1007/s00216-009-3360-1
Baer DR, MH Engelhard, AR Felmy, JJ Ford, JZ Hu, AS Lea, P Nachimuthu, LV Saraf, JA Sears, and S Thevuthasan. 2009. "New Approaches for Characterizing Sensor and Other Modern Complex Materials." ECS Transactions 19(6):137-148. doi:10.1149/1.3118546
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, P Munusamy, and BD Thrall. 2016. "Provenance information as a tool for addressing engineered nanoparticle reproducibility challenges." Biointerphases 11(4):Article No. 04B401. doi:10.1116/1.4964867
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, KL Tsemekhman, SB Baden, JH Weare, and H Jonsson. 2011. "Parallel Implementation of Gamma-Point Pseudopotential Plane-Wave DFT with Exact Exchange." Journal of Computational Chemistry 32(1):54-69.
Bylaska EJ, M Dupuis, and PG Tratnyek. 2008. "One-Electron-Transfer Reactions of Polychlorinated Ethylenes: Concerted and Stepwise Cleavages." Journal of Physical Chemistry A 112(16):3712-3721.
Bylaska EJ, M Dupuis, and PG Tratnyek. 2008. "One-Electron-Transfer Reactions of Polychlorinated Ethylenes: Concerted and Stepwise Cleavages." Journal of Physical Chemistry A 112(16):3712-3721.
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.
Chun CL, DR Baer, DW Matson, JE Amonette, and RL Penn. 2010. "Characterization and Reactivity of Iron Nanoparticles Prepared with Added Cu, Pd, and Ni." Environmental Science & Technology 44(13):5079-5085.
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
Nurmi J, V Sarathy, PG Tratnyek, DR Baer, JE Amonette, and AJ Karkamkar. 2011. "Recovery of Iron/Iron Oxide Nanoparticles from Solution: Comparison of Methods and their Effects." Journal of Nanoparticle Research 13(5):1937-1952. doi:10.1007/s11051-010-9946-x
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.
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, J Antony, and Y Qiang. 2009. "Morphology and Electronic Structure of the Oxide Shell on the Surface of Iron Nanoparticles." Journal of the American Chemical Society 131(25):8824–8832. doi:10.1021/ja900353f
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
Windus TL, EJ Bylaska, K Tsemekhman, J Andzelm, and N Govind. 2009. "Computational Nanoscience with NWChem." Journal of Computational and Theoretical Nanoscience 6(6 SP ISS):1297-1304.