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Title: Final Report: “Energetics of Nanomaterials”

Abstract

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of composition and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.

Authors:
 [1];  [2];  [3]
  1. Brigham Young Univ., Provo, UT (United States)
  2. Univ. of California, Davis, CA (United States)
  3. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
Brigham Young Univ., Provo, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC22)
OSTI Identifier:
1312846
Report Number(s):
DOE-BYU-15666
TRN: US1700262
DOE Contract Number:
FG02-05ER15666
Resource Type:
Technical Report
Resource Relation:
Related Information: B. Huang, J. Schliesser, R.E. Olsen, S.J. Smith, and B.F. Woodfield, "Synthesis and Thermodynamics of Porous Metal Oxide Nanomaterials", Curr. Inorg. Chem. 4, 4053 (2014).M.K. Mardkhe, B.F. Woodfield, C.H. Bartholomew, and B. Huang, "A Method of Making Highly Porous, Stable Aluminum Oxides Doped with Silicon", U.S. (2014).R.E. Olsen, J.S. Lawson, N. Rohbock, and B.F. Woodfield, "Practical Comparison of Traditional and Definitive Screening Designs in Chemical Process Development", International Journal of Experimental Design and Process Optimisation, In Press (2016).N. Liu, X. Guo, A. Navrotsky, L. Shi, and D. Wu, “Thermodynamic Complexity of Sulfated Zirconia Catalysts” J. Catal., In Press (2016).B.F. Woodfield, S. Liu, J. BoerioGoates, and Q. Liu, "Preparation of Uniform Nanoparticles of UltraHigh Purity Metal Oxides, Mixed Metal Oxides, Metals, and Metal Alloys", U.S. 8,211,388 (2012).B.F. Woodfield, C.H. Bartholomew, K. Brunner, W. Hecker, X. Ma, F. Xu, and L. Astle, "Iron and Cobalt Based FisherTropsch PreCatalysts and Catalysts", U.S. 9,114,378 (2015).B.F. Woodfield, S.J. Smith, D.A. Selk, C.H. Bartholomew, X. Ma, F. Xu, R.E. Olsen, and L. Astle, "Single Reaction Synthesis of Texturized Catalysts", U.S. 9,079,164 (2015).C.H. Bartholomew, B.F. Woodfield, B. Huang, B. Olsen, and L. Astle, "A Method for Making Highly Porous, Stable Metal Oxides with Controlled Pore Structure", U.S. 9,334,173 (2016).M.K. Mardkhe, B.F. Woodfield, C.H. Bartholomew, and B. Huang, "A Method of Making Highly Porous, Stable Aluminum Oxides Doped with Silicon", U.S. Allowed (2016).
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; NANOMATERIALS; NANOPARTICLES; NEUTRON REACTIONS; NEUTRON DIFFRACTION; PARTICLE SIZE; SOLUTIONS; SPECIFIC HEAT; WATER; INELASTIC SCATTERING; HEAT; CALORIMETRY; STABILITY; SURFACES; THERMODYNAMICS; SURFACE ENERGY; THERMOCHEMICAL PROCESSES; PHONONS; SPECTRA; PORE STRUCTURE; ALUMINIUM OXIDES; TITANIUM OXIDES; Confinement; GuestHost Interactions; Energy Hydration

Citation Formats

Woodfield, Brian F., navrotsky, alexandra, and Ross, Nancy. Final Report: “Energetics of Nanomaterials”. United States: N. p., 2016. Web. doi:10.2172/1312846.
Woodfield, Brian F., navrotsky, alexandra, & Ross, Nancy. Final Report: “Energetics of Nanomaterials”. United States. doi:10.2172/1312846.
Woodfield, Brian F., navrotsky, alexandra, and Ross, Nancy. 2016. "Final Report: “Energetics of Nanomaterials”". United States. doi:10.2172/1312846. https://www.osti.gov/servlets/purl/1312846.
@article{osti_1312846,
title = {Final Report: “Energetics of Nanomaterials”},
author = {Woodfield, Brian F. and navrotsky, alexandra and Ross, Nancy},
abstractNote = {Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of composition and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.},
doi = {10.2172/1312846},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 8
}

Technical Report:

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  • Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less
  • Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of compositionmore » and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.« less
  • This project, "Energetics of Nanomaterials," represents a three-year collaboration among Alexandra Navrotsky (UC Davis), Brian Woodfield and Juliana Boerio-Goates (BYU), and Frances Hellman (UC Berkeley). It's purpose has been to explore the differences between bulk materials, nanoparticles, and thin films in term of their thermodynamic properties, with an emphasis on heat capaacities and entropies, as well as enthalpies. the three groups have brought very different expertise and capabilities to the project. Navrotsky is a solid-state chemist and geochemist, with a unique Thermochemistry Facility emphasizing enthalpy of formation measurements by high temperature oxide melt and room temperatue acid solution calorimetry. Boerio-Goatesmore » and Woodfield are calorimetry. Hellman is a physicist with expertise in magnetism and heat capacity measurements using microscale "detector on a chip" calorimetric technology that she pioneered. The overarching question of our work is "How does the free energy play out in nanoparticles?", or "How do differences in free energy affect overall nanoparticle behavior?" Because the free energy represents the temperature-dependent balance between the enthalpy of a system and its entropy, there are two separate, but related, components to the experimental investigations: Solution calorimetric measurements provide the energetics and two types of heat capacity measurements the entropy. We use materials that are well characterized in other ways (structurally, magnetically, and chemically), and samples are shared across the collaboration.« less
  • This project, ''Energetics of Nanomaterials'', represents a three-year collaboration among Alexandra Navrotsky (University of California at Davis), Brian Woodfield and Juliana Boerio-Goates (Brigham Young University) and Frances Hellman (University of California at San Diego). Its purpose has been to explore the differences between bulk materials, nanoparticles, and thin films in terms of their thermodynamic properties, with an emphasis on heat capacities and entropies, as well as enthalpies. We used our combined experimental techniques to address the following questions: How does energy and entropy depend on particle size and crystal structure? Do entropic differences have their origins in changes in vibrationalmore » densities of states or configurational (including surface configuration) effects? Do material preparation and sample geometry, i.e., nanoparticles versus thin films, change these quantities? How do the thermodynamics of magnetic and structural transitions change in nanoparticles and thin films? Are different crystal structures stabilized for a given composition at the nanoscale, and are the responsible factors energetic, entropic, or both? How do adsorption energies (for water and other gases) depend on particle size and crystal structure in the nanoregime? What are the energetics of formation and strain energies in artificially layered thin films? Do the differing structures of grain boundaries in films and nanocomposites alter the energetics of nanoscale materials? Of the several directions we first proposed, we initially concentrated on a few systems: TiO(sub 2), CoO, and CoO-MgO. In these systems, we were able to clearly identify particle size-dependent effects on energy and vibrational entropy, and to separate out the effect of particle size and water content on the enthalpy of formation of the various TiO(sub 2) polymorphs. With CoO, we were able to directly compare nanoparticle films and bulk materials; this comparison is important because films can be either 2 dimensional structures, limited by thickness, or can be dominated by nanoparticle granular behavior. These materials represent good model systems which are relevant to technological and geochemical applications as well as to the fundamental underlying science. The collaboration was both congenial and fruitful. We exchanged both samples and scholars among the laboratories. We met several times a year, rotating these meetings among the three institutions. We had frequent conference calls and were in constant email contact. We learned an immense amount from each other because we brought not just different methodologies but different disciplines to the project. In particular, the interplay of physics (Hellman), chemistry (Woodfield, Boerio-Goates, Navrotsky) and geochemistry (Navrotsky) viewpoints has been very enriching. The result has been a number of publications already in print, and several more in preparation, graduate student PhD and MS degrees, and undergraduate research students supported, as well as a well-developed collaboration that will lead to even more fruitful and important science in the coming years.« less
  • This project represents a three-year collaboration among Alexandra Navrotsky, Brian Woodfield, Juliana Bocrio-Goates and Frances Hellman. It's purpose has been to explore the differences between bulk materials, nanoparticles, and thin films in terms of their thermodynamic properties, with an emphasis on heat capacities and entropies, as well as enthalpies. The three groups have brought very different expertise and capabilities to the project. Navrotsky is a solid-state chemist and geochemist, with a unique Thermochemistry Facility emphasizing enthalpy of formation measurements by high temperature oxide melt and room temperature acid solution calorimetry. Bocrio-Goates and Woodfield are physical chemists with unique capabilities inmore » accurate cryogenic heat capacity measurements using adiabatic calorimetry. Hellman is a physicist with expertise in magnetism and heat capacity measurements using microscale ''detector on a chip'' calorimetric technology that she pioneered. The overarching question of the work is ''How does the free energy play out in nanoparticles''? or ''How do differences in free energy affect overall nanoparticle behavior''? Because the free energy represents the temperature-dependent balance between the enthalpy of a system and its entropy, there are two separate, but related, components to the experimental investigations: Solution calorimetric measurements provide the energetics and two types of heat capacity measurements the entropy. They use materials that are well characterized in other ways (structurally, magnetically, and chemically), and samples are shared across the collaboration.« less