Bulletin of the American Physical Society
2009 APS March Meeting
Volume 54, Number 1
Monday–Friday, March 16–20, 2009; Pittsburgh, Pennsylvania
Session W27: Hydrogen Storage: Sorbents |
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Sponsoring Units: FIAP Chair: Channing Ahn, California Institute of Technology Room: 329 |
Thursday, March 19, 2009 11:15AM - 11:27AM |
W27.00001: Functionalized Heterofullerenes for Hydrogen Storage Puru Jena, Qian Wang, Qiang Sun Using density functional theory we show that Li decorated B doped heterofullerene (Li12C48B12) has the desired properties of a hydrogen storage material: (1) The Li atoms remain isolated. (2) Through charge transfer to electron deficient C48B12 heterofullerene, the Li atoms become positively charged. (3) Each Li atom is able to bind up to three H2 molecules which remain in molecular form, and the binding energies of successive H2 molecules are in the range of 0.135 to 0.172 eV/H2, suitable for ambient temperature storage; (4) The gravimetric density reaches the 9 wt {\%} limit necessary for applications in the mobile industry. [Preview Abstract] |
Thursday, March 19, 2009 11:27AM - 11:39AM |
W27.00002: Can Silicon Carbide Nanotubes Be Effective Storage Medium for Hydrogen Storage Souptik Mukherjee, Asok Ray A systematic study of molecular hydrogen adsorption on three different atomic configurations of armchair SICNTs has been performed. In the first stage of our study, first principles calculations using both density functional theory (DFT) and hybrid density functional theory (HDFT) as well as the finite cluster approximation have been performed to study the adsorption of molecular hydrogen on three types of armchair (9, 9) silicon carbide nanotubes. The distances of molecular hydrogen from the outer wall of the nanotubes have been optimized manually using the B3LYP and PW91 functionals and results have been compared in detail with published literature results. In the second part of our study, hydrogen molecule has been adsorbed from both inside as well as from the outer wall of nanotubes ranging from (3, 3) to (6, 6) for all three types. A detailed comparison of the binding energies, equilibrium positions and Mulliken charges has been performed for all three types of nanotubes and for all possible sites in those nanotubes. In the third phase, co-adsorption of two hydrogen molecules has been carried out. Possibilities of hydrogen storage have been explored in detail. [Preview Abstract] |
Thursday, March 19, 2009 11:39AM - 11:51AM |
W27.00003: Nanostructured Adsorbents for Hydrogen Storage Lin Simpson To meet the DOE goals for hydrogen storage, NREL and our partners have focused development efforts on the use of nanomaterials with hydrogen binding energies between $\sim $4 and 40 kJ/mol. The use of these types of materials enables hydrogen to be reversibly adsorption/desorption with moderate to low temperatures and pressures, and greatly simplifies the refueling/ regeneration process. NREL is investigating multiple approaches to obtain high hydrogen sorption materials with the common goal of determining the underlying mechanisms and applying a fundamental basis to intelligently design advanced materials. NREL will provide detailed hydrogen capacity/performance and reproducible processing information for promising nanostructured materials. This will include detailing the potential for hydrogen storage by nanostructures, the effects of dopants, demonstrate materials with greater than 4 wt{\%} hydrogen uptake, and discuss the potential to develop materials with 9 wt{\%} or more hydrogen storage. [Preview Abstract] |
Thursday, March 19, 2009 11:51AM - 12:03PM |
W27.00004: A comparative investigation of H$_2$ adsorption energy in Cd- and Zn-based metal organic framework-5 Pornjuk Srepusharawoot, Carlos Moys\'{e}s Ara\'{u}jo, Andeas Blomqvist, Ralph Scheicher, Rajeev Ahuja Density functional theory has been used to study the physisorption energies of hydrogen at all possible adsorption sites near the metal oxide cluster in both Cd- and Zn-based Metal Organic Framework-5 (MOF-5). Three types of exchange- correlation functionals (LDA, GGA-PW91, and GGA-PBE) were compared. The binding for all adsorption sites in Cd-based MOF- 5 was found to be generally stronger than in Zn-based MOF-5. In particular, the hydrogen adsorption energy at the secondary adsorption sites of Cd-based MOF-5 is increased by about 25\% compared to Zn-based MOF-5. This result suggests that Cd-based MOF-5 might be better suited to store hydrogen at a given temperature than Zn-based MOF-5. See also: {\it J. Chem. Phys.} {\bf 129}, 164104 (2008). [Preview Abstract] |
Thursday, March 19, 2009 12:03PM - 12:15PM |
W27.00005: Design of Multi-Decker Incorporated Metal Organic Frameworks for Hydrogen Storage Kiran Boggavarapu, Anil Kandalam Metal Organic Frameworks (MOFs) are a new class of rationally designed microporous hybrid (organic-inorganic) materials. They have recently gained attention as potential hydrogen storage systems with gravimetric density meeting the DOE 2015 targets of 9 wt{\%}. However, due to weak interaction between the molecular hydrogen and the host MOF (see figure), high pressures are required to reach the target storage levels. Recently, multi-decker organometallic complexes are shown to exhibit the ideal thermodynamics and kinetics for hydrogen storage. However, it is not clear if these multi-decker complexes can retain their hydrogen storage capability when assembled into a bulk-material. In this presentation, we investigate the hydrogen storage capability of a new class of materials by combining the strengths of MOFs and decker complexes. An ideal way to integrate these two systems is to incorporate the multi-deckers into the structural framework of MOFs. In these hybrid materials, the multi-decker units are expected to maintain their structural integrity and there by retaining the hydrogen storage capacity with an added advantage of being a part of stable porous MOF back-bone. [Preview Abstract] |
Thursday, March 19, 2009 12:15PM - 12:27PM |
W27.00006: Hydrogen Adsorption by High Surface Area Micro- porous Carbon Synthesized from Phenol-Formaldehyde Qingyuan Hu, Gregory P. Meisner A high surface area microporous carbon material can be synthesized by mixing the activation reagent potassium hydroxide into a carbon precursor solution of phenol-formaldehyde oligomers. Some polymerization of the carbon precursor occurs during the initial mixing, and further polymerization is completed by heating to 160$^{o}$C. Carbonization and activation is accomplished by heating to 500$^{o}$C - 900$^{o}$C in an inert atmosphere. The porosity and surface area of the resulting carbon material depends predominantly on the amount of activation reagent added to the carbon precursor solution and on the carbonization/activation temperature and time. Optimized synthesis conditions yield a microporous carbon with a very high BET specific surface area of nearly 3000 m$^{2}$/g and a narrow pore size distribution. This new synthesis approach yields surface areas dramatically larger than those typically obtained by traditional chemical activation methods for porous carbon where solid carbon precursors are soaked in activation reagent solutions. Hydrogen absorption up to 5.75 wt{\%} at 77 K and above 20 bars hydrogen pressure is observed for this new microporous carbon material. [Preview Abstract] |
Thursday, March 19, 2009 12:27PM - 12:39PM |
W27.00007: Ab-initio study of hydrogen storage of Titanium-decorated organic systems with hydroxyl groups Manh Cuong Nguyen, Jisoon Ihm Using first-principles calculation, we study hydrogen storage of Titanium-decorated organic systems with hydroxyl groups, such as propane-1,3-diol. The results show that Ti atom is bound selectively to hydroxyl groups with the binding energy of 3.0 eV. The first hydrogen molecule adsorbed on Ti is dissociated and then Ti can bind three hydrogen molecules in molecular form more with the binding energy suitable for reversible processes (adsorption and desorption) in hydrogen storage at ambient temperature and pressure. Using thermodynamics, the usable number of hydrogen molecules per Ti atom is almost three due to the proper binding energy of the last three hydrogen molecules on Ti. Based on this result, we can design organic systems with hydroxyl groups to store hydrogen with the reduction of the tendency of transition metal clustering. We also explain the mechanism of multi-hydrogen molecules adsorption on Ti by generalizing the Kubas model. [Preview Abstract] |
Thursday, March 19, 2009 12:39PM - 12:51PM |
W27.00008: First-principles study of dihydrogen interaction of porphyrin-like nitrogen-doped graphenes Woon Ih Choi, Seung-Hoon Jhi, Yong-Hyun Kim We have studied electronic structure and dihydrogen (H$_{2})$ binding characteristics of porphyrin-like nitrogen-doped graphenes (PNGs) by performing first-principles total energy calculations based on the density functional theory. The stability of PNGs and the H$_{2}$ binding ability of the PNG metal centers (Ca and 3$d$ transition metals from Sc to Zn) have been analyzed within the generalized gradient approximation. We have found that Ca, Sc, Ti, Co, and Ni can be incorporated relatively easily into the nitrogen-doped graphenes, while V, Fe, Cu, and Zn are less likely to be. The PNGs can be used for active building blocks of hydrogen storing metal-organic frameworks. Due to the unique crystal field splitting of the planar PNGs, approaching dihydrogen exclusively interacts with the $d$z$^{2}$ orbitals of the core metals. We also found that intra-$d$-orbital charge transfer plays a key role in the dihydrogen binding. Finally, we will discuss how such dihydrogen binding can be modified by external strain. [Preview Abstract] |
Thursday, March 19, 2009 12:51PM - 1:03PM |
W27.00009: Magnetic Properties of High-Surface-Area Carbons and Their Effect on Adsorbed Hydrogen Jimmy Romanos, Matthew Beckner, Michael Kraus, Jacob Burress, Peter Pfeifer We report the discovery that a large number of nanoporous carbon samples, made from corn cob and exhibiting high hydrogen storage capacities (Pfeifer et al, Mater. Res. Soc. Symp. Proc. 1041 R02-02 (2008)), show unexpected magnetic properties, due to iron impurities in the samples. Magnetization curves are consistent with ferromagnetic and/or super-paramagnetic behavior. Magnetic susceptibilities, saturation magnetizations, coercivities and remanence magnetizations, from measurements on a SQUID magnetometer, will be presented, and their temperature dependence will be discussed. Results will be presented regarding the presence of small iron clusters, magnetic properties of iron-leached samples, and hydrogen binding energies as a function of iron leaching. This material is based on work supported by the U.S. Department of Energy under Award No. DE-FG-08GO18142. [Preview Abstract] |
Thursday, March 19, 2009 1:03PM - 1:15PM |
W27.00010: Boron-Doped Carbon Nanospaces for High-Capacity Hydrogen Storage Matthew Beckner, Jacob Burress, Carlos Wexler, Zhi Yang, Fred Hawthorne, Peter Pfeifer The Alliance for Collaborative Research in Alternative Fuel Technology (ALL-CRAFT, http://all-craft.missouri.edu) has been optimizing high surface area [$>$3,000 m2/g] activated carbon nanospaces for high capacity hydrogen storage. Boron-doped samples have been produced using solid, liquid, and vapor phase boron doping. The boron-doped samples were analyzed using sub-critical nitrogen adsorption to determine surface areas and the effect that boron-doping and annealing, as a function of temperature, has on the microporous structure of the samples. Results will be presented for hydrogen storage capacity (excess adsorption) per unit area of boron-doped surface, and for hydrogen binding energies at 77 K and 293 K, as a function of boron concentration and annealing temperature. This material is based on work supported by the U.S. Department of Defense under Awards No. N00164-07-P-1306 and N00164-08-C-GS37. [Preview Abstract] |
Thursday, March 19, 2009 1:15PM - 1:27PM |
W27.00011: Hierarchical Pore Structure of Engineered Carbon Nanospaces for Use in Hydrogen Storage. Michael Kraus, Jacob Burress, Matthew Beckner, Carlos Wexler, Peter Pfeifer High-surface-area activated carbons are promising material for hydrogen storage. Mapping the pore structure at the nanometer scale is fundamental for the understanding of adsorptive properties. Structural analyses of pore spaces in nanoporous carbons, using subcritical nitrogen adsorption, supercritical methane adsorption, and small-angle x-ray scattering (SAXS), are presented. Adsorption isotherms provide pore-size distributions, while SAXS provides information about the spatial arrangement of pores. At large length scales, $\sim $20-2000 nm, our samples exhibit an extended regime of surface fractal behavior with a fractal dimension of $\sim $2.3, corresponding to a mild external roughness of the samples. At small length scales, the samples exhibit an abundance of pores 0.5-1.5 nm wide. An illustrative case exhibits cylindrical pores with average width of 0.9 nm and average length 1.6 nm, in excellent agreement with structural data inferred from adsorption isotherms. Comparison of pore data from SAXS and nitrogen isotherms will be compared with hydrogen uptake isotherms. This material is based on work supported by the U.S. Department of Energy under Award No. DE-FG-08GO18142. Use of the Advanced Photon Source was supported by the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. [Preview Abstract] |
Thursday, March 19, 2009 1:27PM - 1:39PM |
W27.00012: Analysis of Hydrogen Adsorption in Engineered Carbon Nanospaces Jacob Burress, Matthew Beckner, Nick Kullman, Raina Cepel, Carlos Wexler, Peter Pfeifer We present a survey of how appropriately engineered nanoporous carbons provide materials for reversible hydrogen storage, based on physisorption, with exceptional storage capacities ($\sim $80 g H2/kg carbon, $\sim $50 g H2/liter carbon, at 50 bar and 77 K). The H2 gas-carbon surface interface physics was investigated using supercritical hydrogen isotherms. Experimental case studies, with surface areas as high as 3500 m2/g, in which 40{\%} of all surface sites reside in pores of width $\sim $0.7 nm and binding energy $\sim $9 kJ/mol, and 60{\%} of sites in pores of width $>$1.0 nm and binding energy $\sim $5 kJ/mol, are also presented. We experimentally distinguish between molecules exhibit mobile or local adsorption, how lateral dynamics affect the hydrogen storage capacity, and how the two situations are controlled by the vibrational frequencies of adsorbed hydrogen molecules parallel and perpendicular to the surface. In our samples, adsorption is mobile at 293 K, and localized at 77 K. These findings present evidence hydrogen storage capacities in nanoporous carbons can be increased, without any chemical surface functionalization, by more than a factor of two by suitable engineering of the nanopore space. This material is based on work supported by the U.S. Department of Energy under Award No. DE-FG02-07ER46411. [Preview Abstract] |
Thursday, March 19, 2009 1:39PM - 1:51PM |
W27.00013: Quantum energy levels of hydrogen adsorbed on nanoporous carbons: an intrinsic probe for pore structure, and improving Monte Carlo simulations of adsorption R. Cepel, B. Kuchta, L. Firlej, P. Pfeifer, C. Wexler Hydrogen is the lightest molecule in nature, making both rotational and translational degrees of freedom eminently quantum mechanical (especially at low temperatures). For isolated molecules the first excited (degenerate) rotational states are at about 175 K above the (non-degenerate) ground state. When the hydrogen molecule is adsorbed, however, interaction with the substrate partially eliminates this degeneracy due to the different adsorption strengths of the different rotational states of the molecule. In this talk, we consider the adsorption of hydrogen in nanometer-size pores in carbon. We show that the rotation-vibration energy levels are strongly dependent on the pore structure (geometry and size). This dependence may be probed by inelastic neutron scattering as a local, non-destructive, probe intrinsic to the system, to characterize nanopores (in fact, using H$_2$ as the probe makes sure that the pore structure probed is relevant for H$_2$ adsorption). The rotation-vibration energy levels were also used as input for grand canonical Monte Carlo simulations of H$_2$ adsorption, improving the accuracy of the simulations. [Preview Abstract] |
Thursday, March 19, 2009 1:51PM - 2:03PM |
W27.00014: Structural and energetic factors in designing a perfect nano-porous sorbent for hydrogen storage Bogdan Kuchta, Lucyna Firlej, Raina Cepel, Peter Pfeifer, Carlos Wexler Carbons are one of potentially promising groups of materials for hydrogen storage by adsorption. However, the heat of hydrogen physisorption in such materials is low, in the range of about 4-8 kJ/mol which limits the total amount of hydrogen adsorbed at P = 100 bar to $\sim$2 wt\% at room temperature and about $\sim$10 wt\% at 77 K. To get better storage capacity, the adsorbing surfaces must be modified, either by substitution of some atoms in the all-carbon skeleton by other elements, or by doping/intercalation with other species. Here we analyze the variation of interaction energy between a molecule of hydrogen and graphene-based sorbents prepared as hypothetical modifications of the graphene layer. In particular, we show that partial substitution of carbons (for example, by boron) modifies both the symmetry of the energy landscape and strength of hydrogen physisorption. The effect of substituent extends over several sites of graphene lattice making the surface more heterogeneous. [Preview Abstract] |
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