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Title: Size-dependent structure of silver nanoparticles under high pressure

Abstract

Silver noble metal nanoparticles that are<10 nm often possess multiply twinned grains allowing them to adopt shapes and atomic structures not observed in bulk materials. The properties exhibited by particles with multiply twinned polycrystalline structures are often far different from those of single-crystalline particles and from the bulk. I will present experimental evidence that silver nanoparticles<10 nm undergo a reversible structural transformation under hydrostatic pressures up to 10 GPa. Results for nanoparticles in the intermediate size range of 5 to 10 nm suggest a reversible linear pressure-dependent rhombohedral distortion which has not been previously observed in bulk silver. I propose a mechanism for this transitiion that considers the bond-length distribution in idealized multiply twinned icosahedral particles. Results for nanoparticles of 3.9 nm suggest a reversible linear pressure-dependent orthorhombic distortion. This distortion is interpreted in the context of idealized decahedral particles. In addition, given these size-dependent measurements of silver nanoparticle compression with pressure, we have constructed a pressure calibration curve. Encapsulating these silver nanoparticles in hollow metal oxide nanospheres then allows us to measure the pressure inside a nanoshell using x-ray diffraction. We demonstrate the measurement of pressure gradients across nanoshells and show that these nanoshells have maximum resolved shear strengthsmore » on the order of 500 MPa to IGPa.« less

Authors:
 [1]
  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
978860
Report Number(s):
LBNL-2382E
TRN: US201010%%245
DOE Contract Number:
AC02-05CH11231
Resource Type:
Thesis/Dissertation
Resource Relation:
Related Information: Designation of Academic Dissertation: Doctoral; Academic Degree: PhD; Name of Academic Institution: University of California, Berkeley; Location of Academic Institution: Berkeley, California
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; CALIBRATION; COMPRESSION; DISTRIBUTION; HYDROSTATICS; OXIDES; PRESSURE GRADIENTS; SHEAR PROPERTIES; SILVER; TRANSFORMATIONS; X-RAY DIFFRACTION; silver nanoparticles; structural distortions; high pressure; diamond anvil cell; hollow nanospheres

Citation Formats

Koski, Kristie Jo. Size-dependent structure of silver nanoparticles under high pressure. United States: N. p., 2008. Web. doi:10.2172/978860.
Koski, Kristie Jo. Size-dependent structure of silver nanoparticles under high pressure. United States. doi:10.2172/978860.
Koski, Kristie Jo. 2008. "Size-dependent structure of silver nanoparticles under high pressure". United States. doi:10.2172/978860. https://www.osti.gov/servlets/purl/978860.
@article{osti_978860,
title = {Size-dependent structure of silver nanoparticles under high pressure},
author = {Koski, Kristie Jo},
abstractNote = {Silver noble metal nanoparticles that are<10 nm often possess multiply twinned grains allowing them to adopt shapes and atomic structures not observed in bulk materials. The properties exhibited by particles with multiply twinned polycrystalline structures are often far different from those of single-crystalline particles and from the bulk. I will present experimental evidence that silver nanoparticles<10 nm undergo a reversible structural transformation under hydrostatic pressures up to 10 GPa. Results for nanoparticles in the intermediate size range of 5 to 10 nm suggest a reversible linear pressure-dependent rhombohedral distortion which has not been previously observed in bulk silver. I propose a mechanism for this transitiion that considers the bond-length distribution in idealized multiply twinned icosahedral particles. Results for nanoparticles of 3.9 nm suggest a reversible linear pressure-dependent orthorhombic distortion. This distortion is interpreted in the context of idealized decahedral particles. In addition, given these size-dependent measurements of silver nanoparticle compression with pressure, we have constructed a pressure calibration curve. Encapsulating these silver nanoparticles in hollow metal oxide nanospheres then allows us to measure the pressure inside a nanoshell using x-ray diffraction. We demonstrate the measurement of pressure gradients across nanoshells and show that these nanoshells have maximum resolved shear strengths on the order of 500 MPa to IGPa.},
doi = {10.2172/978860},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2008,
month =
}

Thesis/Dissertation:
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  • Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10 -6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C 6H 11) and π-allyl Cmore » 6H 9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C 6H 9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C 6H 9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E 2u mode of free benzene, which leads to catalysis. Linear C 6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt(100). Based on spectroscopic signatures, mechanisms for catalytic isomerization and dehydrocyclization of n-hexane were identified. The structure sensitivity of benzene hydrogenation on shape controlled platinum nanoparticles was also studied. The nanoparticles showed similar selectivities to those found for Pt(111) and Pt(100) single-crystals. Additionally, the nanoparticles have lower activation energies than their single-crystal counterparts.« less
  • This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF 6 -, RuF 6 -, or RhF 6 -, Ag(III)more » solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF 6 - to IrF 6 at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag 2+ (MF 6 - 2 salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag 2+. The anion must also be a poor F - donor; otherwise, either AgF + salts or AgF 2 are generated.« less
  • Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.