John B. Parise
Ph.D., James Cook University, 1981
Lecturer, University of Sydney, 1986-87
Visiting Scientist, E.I. DuPont, 1981-83, 1988-89
Faculty member at Stony Brook since 1989
Professor Parise is a mineralogist and solid-state chemist interested in Earth materials synthesis and the determination of atomic arrangements in condensed matter. The Parise group maintains an eclectic mix of projects, tied together by one guiding principal: We care about where the atoms are, and where they end up after changes in environmental conditions. No matter what the particular composition of the condensed matter its functionality is dependent on where the atoms are and where they end up after they respond to changes in P, T, Eh, pH, etc) - think graphite - diamond, Ice - water, DNA to remind yourselves of the fundamental need to determine where the atoms are under the operating conditions of interest. With that appreciation, the tools developed to study the mineralogy and reactivity in extreme Earth environments are often applicable to technologically interesting materials and materials in extra-terrestrial environments.
The group places a strong emphasis on synthesis and students make the samples they later characterize.
The structure of liquids, nano-crystalline and amorphous materials:
Increasingly, solutions proposed to a number of technological challenges in the energy sector involve the synthesis and/or use of disordered materials, including liquids, melts, nano- and glassy materials, at extreme conditions. Examples include materials under high radiation fluxes advanced nano-materials for energy storage and conversion, clathrates and other materials in contact with sequestered carbon - supercritical CO 2 in reservoirs or the deep ocean, for example, and high energy density materials. Understanding how the atomic arrangements in this class of materials respond to changes in pressure (p), temperature (T) gas loading and high chemical gradients is therefore fundamental to 1) understanding the behavior of these materials under their operating conditions, and 2) deriving general principles applicable to such classes of materials that 3) can be applied to vary conditions of manufacture that "steer" toward the desired product. Addressing our energy-related problems will therefore involve learning how to vary reaction pathways, including those at extreme conditions, in order to obtain precise information on changes in structural arrangements in situ. We combine development of sample cells for in situ x-ray and neutron (XN) scattering of key classes of materials under their operating conditions, with innovative data analysis and modeling in order to characterize materials with intrinsic disorder, such as are encountered in nano-, melt, glassy and gas adduct materials. We do this in collaboration with partners in industry at the Advanced Photon Source (APS) at Argonne National Laboratory (ANL) in Chicago, at the National Synchrotron Light Source-II (NSLS-II) at Brookhaven National Laboratory (BNL) some30 minutes from the Stony Brook University (SBU) campus, and at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) in Tennessee.
The "structure" of UO2 in solid and molten forms:
A recent study of UO 2 melt is illustrative of the philosophy of choosing difficult first order problems and using scattering and analysis to provide fundamental insights into behavior and properties. The motivation for this study is the extensive use of uranium dioxide (UO 2) as the major fuel component for most nuclear power reactors in use today (even mixed oxide (MOX) fuel is typically 90wt% UO 2). A key safety concern in nuclear accidents is the melting and subsequent leakage of fuel. However the very high melting temperature (3140K) has limited study of the liquid phase. Consequently, relatively little is known about the atomic structure of molten UO 2, and to our knowledge no detailed diffraction measurements have been made.
Whilst several empirical potential Molecular Dynamics (MD) models exist for UO 2 , these are often constructed from fitting to low temperature crystal phases. The temperature-range of applicability of these models is often limited, and in the absence of measurements their relevance to the liquid structure remains un- validated. In UO 2 ,the extension of empirical MD models is also complicated by the pre-melting lambda transition: The liquid is likely to be more similar to the post transition solid, than to the lower-temperature solid, from which most MD potentials are derived; MD simulation is used to derive such important parameters as viscosity, and so validation of potentials using the liquid scattering function above the melting point is a primary measurement that will validate potentials.
Top: Phase diagram around the melting point of UO 2. Bottom: Heat capacity and conductivity of UO 2 approaching the superionic lambda transition at 2670K
Highlight articles referring to this work, published in Science (Skinner, L. B.; Benmore, C. J.; Weber, J. K. R.; Williamson, M. A.; Tamalonis, A.; Hebden, A.; Wiencek, T.; Alderman, O. L. G.; Guthrie, M.; Leibowitz, L.; Parise, J. B. Molten uranium dioxide structure and dynamics Science 2014, 346, 984-987) can be found here:
We leveraged developments in high-powered laser heating and aerodynamic levitation detector corrections and experience with general rules recently derived for the behavior of oxide melts. The levitation technique involves the floating of a 3mm ball-shaped sample on an upwards gas stream. The absence of a solid contact surface allows the chemical purity of the very hot sample to be maintained. Also a low oxygen atmosphere will be needed to avoid 3(UO 2) + O 2 → U 3O 8 at 970 K. A short summary of results is provided in the highlights.The scientific program is underpinned by sound technical developments now that now allow us to study a variety of important disordered materials in situ, over a wide range of conditions, with unprecedented precision. Novel cell-design will be particularly important as operations begin at NSLS-II.
The first structure measurements of molten UO 2 at 3000°C have been carried out recently at the APS. These experiments were enabled by development of atmosphere controlled levitation and laser heating techniques. UO 2 is the primary ingredient for nuclear fuel. Working with very hot liquids is technically challenging. The new structure data will advance models used to predict properties and behavior of UO 2 at extreme conditions. Samples were levitated in high purity argon and heated to 3000 °C with a 400 W CO2 laser. The structure of the liquid was measured in-situ using a 111 keV x-ray beam. Data were acquired using an area x-ray detector with fast data acquisition. Analysis was performed using custom software developed as part of this project.
The structure of water around the compressibility minimum:
Water is the universal solvent, and as such plays a central role in the processing of many ceramics, especially using chemie douce techniques such as sol-gel. The behavior of water as a function of temperature, pressure (positive and negative) electric field etc is central to efforts directed toward controlling processing parameters . Generally liquids contract and become less compressible upon cooling, water, however, becomes more compressible below 46.5 oC. Here we show this well-known phenomenon takes place in the same temperature region as continuous structural changes in the second nearest neighbor oxygen-oxygen (O-O) peak of the pair distribution function, obtained through the measurement of high energy x-ray diffraction data out to high momentum transfers ( 𝑄). The structure of water and molecular arrangements in water at distances beyond the first nearest neighbor has been debated since the first x-ray measurements were made and this continues to the present day. In addition, the density dependent O-O network topology of water has been found to be similar to that of tetrahedral liquids Si and Ge. Our measurements show that the 1 st neighbor O-O peak has a constant coordination of 4.3(2) at atmospheric pressure and follows a linear expansion from -19 oC to 93 oC, which severely constrains any structural model imposed on liquid water.
Engineering frameworks that are tailored to be selective:
Zeolites and synthetic molecular sieves are useful materials for separations technologies. We are interested in not only how natural systems exchange, sequester and release ions, but also in how to apply the knowledge derived from basic science studies of natural systems to synthetic materials as well. The functionality of these as well as naturally occurring materials such as aluminosilicate zeolites, need to be understood in the context of their atomic structures. Separations applicable to the nuclear industry illustrate this point.
Safe storage is a significant bottleneck in the nuclear fuel cycle and further development of the nuclear power industry requires implementation of efficient and economically viable industrial-scale processes that sequester highly radioactive waste during fuel rod reprocessing. Separating and sequestering volatile isotopes of Kr and Xe present special engineering challenges; currently they are captured and separated via energy-intensive cryogenic distillation, a process also used in the industrial production of noble gases from air. As radioactive 131Xe has a half-life of 36.3 days, short-time storage of radioactive Kr/Xe mixtures and later separation of 85Kr (t 1/2 = 10.8 years) from stable Xe will significantly reduce the volume of long-term stored radioactive waste and provide industrially useful Xe. Other gas separations critical to the nuclear industry include hydrogen/deuterium/tritium separation and sequestration of radioactive iodine.
Xe/Kr separation using selective solid state adsorbent is a viable alternative to
cryogenic distillation and many porous materials such as activated carbon, organic
cages, and modified zeolites were extensively tested by experimental and computational
methods. Metal organic frameworks (MOFs) are a relatively new class of materials,
based on metal ions and organic ligands forming microporous frameworks. The variety
of compositions capable of forming MOFs, along with their modification post-synthesis,
facilitates the tailoring of pore geometry and chemistry for specific applications.
Only a handful of noble gas adsorption studies in MOFs are presented in literature.
|(A) Structure of activated SBU2. The colored spheres indicate estimated channel aperture, color-coded: yellow – type-I, green – type-II. (B) Pores running along . The octahedral coordination around calcium are presented as blue polyhedra, oxygen – red spheres and carbon – grey wire bonds. Hydrogen atoms are omitted for clarity.|
The ability to determine the equilibrium structures gas-MOF adducts is well established for single crystal and powder studies. To better understand optimal framework characteristics it is essential to directly study the adsorption mechanism, and experimental structural analysis provides the most detailed picture of adsorbate-adsorbent interactions. We carried out a static study to demonstrate this.
We recently synthesized a robust 3-D porous crystalline MOF (Fig. above) containing calcium and 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, a new MOF named SBU2:H2O (SBU-Stony Brook University). The dehydrated form, SBU2, adsorbs Xe at a capacity of 37.1 wt% at 298 K and with high Xe/Kr selectivity of approximately 10 at 298K; these results are extraordinary for an unmodified MOF. We examined the Xe and Kr adsorption mechanism by interpreting the results of single crystal X-ray diffraction (XRD), and observed significant differences for Xe versus Kr, noting differentiation between polar and non-polar pores in SBU2. Although polar pores occur in other MOFs, the differentiation of sorbed gases between them, as occurs in SBU2, is not reported for MOFs.
Single crystal diffraction results from statically loaded samples indicate Xe ordering with two distinct adsorption sites in channels of type-I and type-II. In channel type-I, Xe is surrounded by H atoms from phenyl rings while in channel type-II the shortest Xe…H distance is to hydroxyl groups. Kr occupies two similar sorption sites as those found for SBU2:Xe, but with longer Kr…H distances than Xe…H, despite Xe’s larger doameter. The observed longer distances between H and Kr in comparison to H and Xe atoms is consistent with the Xe selectivity in SBU2 being driven by larger size and stronger polarizability of Xe atoms compared to Kr. Simulation and experimental breakthrough experiments carried out in conditions expected for spent nuclear fuel reprocessing, suggested preferable adsorption and selectivity towards Xe over Kr by SBU2. Low concentration breakthrough experiments using a gas flow with 400 ppm of Xe and 40 ppm of Kr in He indicated similar Xe/Kr selectivity. These results confirm that the adsorption kinetics in SBU2 is fast enough for separation of Xe over Kr.
- Skinner, L. B.; Benmore, C. J.; Weber, J. K. R.; Williamson, M. A.; Tamalonis, A.; Hebden, A.; Wiencek, T.; Alderman, O. L. G.; Guthrie, M.; Leibowitz, L.; Parise, J. B. Molten uranium dioxide structure and dynamics Science 2014, 346, 984-987.
- Skinner, L. B.; Benmore, C. J.; Parise, J. B. (2012) Comment on 'Molecular arrangement in water: random but not quite' J. Phys.-Condes. Matter, 24, 338001.
- Skinner, L. B.; Benmore, C. J.; Shyam, B.; Weber, J. K. R.; Parise, J. B. (2012) Structure of the floating water bridge and water in an electric field Proc. Natl. Acad. Sci. U. S. A. 109, 16463-16468.
- Skinner, L.B., C.J. Benmore, J.K.R. Weber, J. Du, J. Neuefeind, S.K. Tumber, and J.B. Parise (2014) Low Cation Coordination in Oxide Melts. Physical Review Letters, 112: 157801.
- L. Yang, C. A. Tulk, D. D. Klug, I. L. Moudrakovski, C. I. Ratcliffe, J. A. Ripmeester, B. C. Chakoumakos, L. Ehm, C. D. Martin and J. B. Parise (2009) Synthesis and characterization of a new structure of gas hydrate. Proc. Nat. Acad. Sci. 106, 6060-6064.
- Ehm, L., L.A. Borkowski, J.B. Parise, S. Ghose, and Z. Chen (2011) Evidence of tetragonal nanodomains in the high-pressure polymorph of BaTiO 3. Applied Physics Letters, 98, 021901.
- Jina, H., Plonka, A. M., John B. Parise, Goroff, N. S. (2013) Pressure induced topochemical polymerization of diiodobutadiyne: a single-crystal to single-crystal transformation. CrystEngComm, 15, 3106-3110 (top 20 cited paper in journal 2014).
- Plonka, A. M., Banerjee, D., Woerner, W. R., Zhang, Z., Li, J. and Parise, J. B. (2013) Effect of ligand geometry on selective gas-adsorption: the case of a microporous cadmium metal organic framework with a V-shaped linker, Chem. Commun., 2013, 49 (63), 7055 – 7057.
- Banerjee, D.; Parise, J. B. (2011) Recent Advances in s- Block Metal Carboxylate Networks. Cryst. Growth Des., 11, 4704-4720.
- Plonka, A. M, Banerjee, D. Woerner, W. R., Zhang, Z., Nijem, N., Chabal, Y. J., Li, J. and Parise, J. B. (2013) Mechanism of Carbon Dioxide Adsorption in a Highly Selective Coordination Network Supported by Direct Structural Evidence, Angew. Chem. Int. Ed., 52, 1692 –1695.
- Li, W., Harrington, R. Tang, Y., Kubicki, J. D., Aryanpour, M., Reeder, R. J., Parise, J. B. and Phillips, B. L. (2011) Differential Pair Distribution Function Study of the Structure of Arsenate Adsorbed on Nanocrystalline γ-Alumina, Environ. Sci. Technol., 45, 9687–9692.
- Xu, W. Q.; Parise, J. B.; Hanson, J. (H 3O)Fe(SO 4) 2 formed by dehydrating rhomboclase and its potential existance on Mars Amer. Mineral. 2010, 95, 1408-1412.
- Jolley, C.; Klem, M.; Harrington, R.; Parise, J.; Douglas, T. (2011) Structure and photoelectrochemistry of a virus capsid-TiO 2 nanocomposite Nanoscale, 3, 1004-1007.
- Xu, W. Q.; Parise, J. B. (2011) Synthetic ferric sulfate trihydrate, Fe 2(SO 4) 3.3H 2O, a new ferric sulfate salt Acta Crystallog. C, 67, I30-I32.
- Plonka, A. M., Dera, P., Irmen, P., Rivers, M. L., Ehm, L. and Parise, J. B. (2012) -diopside, a new ultrahigh-pressure polymorph of CaMgSi 2O 6 with six-coordinated silicon, Geophys. Res. Lett., 39, L24307.