An enhanced hydrogen adsorption enthalpy for fluoride intercalated graphite compounds

An Enhanced Hydrogen Adsorption Enthalpy for Fluoride Intercalated
Graphite Compounds
Hansong Cheng,*,† Xianwei Sha,† Liang Chen,‡ Alan C. Cooper,† Maw-Lin Foo,† Garret C. Lau,† Wade H. Bailey III,† and Guido P. Pez† Air Products and Chemicals, Inc., 7201 Hamilton BouleVard, Allentown, PennsylVania 18195, and Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, P. R. China Received September 23, 2009; E-mail: It has been widely recognized that improved hydrogen storage fluorination levels are accessible, and the nature of the C-F bonding devices require new lightweight materials capable of interacting with evolves from ionic to semi-ionic to covalent as the decreasing C:F molecular hydrogen via either physisorption or chemisorption.1,2 This interaction must occur with an appropriate strength to enable the capture We conducted ab initio molecular dynamics (AIMD) simulations of hydrogen to be reversible under practical operating conditions of at room temperature on H2 in a GIC containing fluoride anions and temperature and/or pressure. Porous hydrogen storage materials that subsequently synthesized fluoride GICs for isotherm measurements.
store H2 via physical adsorption have a perceived advantage for system The electronic energies were calculated with periodic density functional heat removal during filling relative to most metal hydrides and chemical theory (DFT) under the local density approximation (LDA) employing hydrides due to the relatively low enthalpy associated with physisorp- the Perdew-Zunger exchange-correlation functional11 coupled with tion. Most hydrogen storage materials in this class rely on physical a plane-wave basis set, while the AIMD simulation was performed in adsorption due to van der Waals forces and/or electron density donation the constant NVE canonic ensemble using the Nose´ thermostat.12 from the σ orbital of H2 to an electrophile (“Kubas-type binding”).3 Details of the computational method, material synthesis, and charac- Here, we report a study of H2 adsorption in graphite intercalation terization can be found in the Supporting Information. The selected compounds (GICs) containing fluoride anions. In contrast to Kubas- unit cell in our simulations contains 32 C and 8 F atoms. For maximum type binding and alkali metal GICs,4 the dominant mechanism of capacity, stage-1 GICs were studied with 1, 2, 12, and 24 H2 molecules hydrogen binding in these materials is donation of electron density per unit cell, corresponding to 0.37-8.22 wt % H2.
from a nucleophile to the σ* orbital of H2. We show that thesecompounds exhibit a higher heat of adsorption at near-ambienttemperatures than other porous H2 storage materials, such as activatedcarbons and metal organic framework (MOF) compounds, and thuscould potentially serve as practical H2 storage media.
In gas-phase calculations, “naked” fluoride anions5 and charge- separated ammonium fluoride salts6 have been shown to interactstrongly with molecular hydrogen. Sweany et al. have reported anexperimental characterization of adducts of H2 with CsF ion pairs.7The normally infrared-silent H2 was perturbed by the salt, yieldingspectra interpreted as arising from H2 and CsF adducts, with as manyas 3 H2 molecules per CsF, where H2 interacts primarily with the F-anion. Based on frequency shifts showing a lengthening of the H-Hbond, the interaction was attributed to the donation of electron density Figure 1. Fully optimized structures of the partially fluorinated GIC (a)
from the F- anion to the H2 antibonding σ* orbital.
and the GIC with 2 H2 (b), 12 H2 (c), and 24 H2 (d).
Fluorous MOF containing covalent C-F bonds exhibited a large Table 1. H2 Gravimetric Density, the Calculated Lattice Spacing,
2 uptake at 77 K, but unusually high H2 adsorption enthalpies were the Average Bader Charge on F, and the Average H not reported.8 Thus, the conceptual challenge is to devise solid-state materials which incorporate both the strong hydrogen interactions of“naked” fluoride and sufficient porosity. Chemical intercalation of graphite has been demonstrated to increase the H by creating porosity through intercalation and separation of the graphene layers as well as increasing the hydrogen affinity of the graphite through increased electron density. For example, the second- stage graphite intercalation complex KC24 has been shown to adsorb2H2/K at 77 K corresponding to 1.2 wt % H2.9 Electron transfer fromK to the graphene layers in this “donor type” GIC increases the heat Upon F- intercalation, significant lattice expansion (∼2.3 Å) occurs, of adsorption from -4 kJ/mol in native graphite to ca. -10 kJ/mol in based upon the DFT structural optimization, and the intercalated F KC24. To date, there have been no examples of “acceptor type” GICs atoms form long C-F bonds with the graphene sheets. Compared to with a demonstrated appreciable hydrogen adsorption. Graphite the typical C-F bond lengths in organofluorine compounds and fluorides represent a well-studied subset of acceptor GICs. A range of perfluorinated graphite (∼1.35 Å), the C-F bonds in the partiallyfluorinated graphite GIC are considerably longer, ranging from 1.417 to 1.533 Å. The significantly elongated, semi-ionic bonds arise from bond angle distortions resulting from the partial fluorination as only 17732 9 J. AM. CHEM. SOC. 2009, 131, 17732–17733
10.1021/ja907232y 2009 American Chemical Society
some of the C atoms change their electronic configuration from sp2 to of the GIC at near-ambient temperatures and the heat of adsorption sp3. As shown in Table 1, Bader population analysis indicates that the are comparable to an MOF incorporating coordinatively unsaturated average charge (QF) on the F atoms ranges from -0.655 to -0.659.
transition metals18 despite the extremely large difference in surface At low H2 loadings, the spacing between adjacent graphene layers shrinks slightly since the H2 molecules interact more strongly with Besides the well-known LDA overbinding,19 the gap between the the semi-ionic F atoms (Table 1). At higher H2 loadings, however, calculated energies at low loading and the experimental heat of the interlayer distance increases substantially to accommodate the large adsorption is likely due to the presence of residual BF4 in the number of H2 molecules. Figure 1 displays the fully equilibrated as-prepared GIC, which dilutes the gravimetric hydrogen density and structures of partially fluorinated GIC and GIC with 2, 12, and 24 H2 adsorption enthalpy. After measuring isotherms on a large number of molecules in the unit cell. A detailed analysis of the AIMD trajectories CxFy(BF4)1-y samples, we found the isosteric heat of adsorption to be indicates that H2 molecules in the lattice interact with the fluoride ions very sensitive to both the C:F ratio and the amount of residual BF4.
but are highly mobile in the interlayer spaces at 300 K. The H2 These variables likely affect the semi-ionic/covalent nature of the C-F molecules are confined to the interlayer spaces between F atoms and bonds and accessibility of H2 to the intercalated fluoride ions. It is are rarely in close contact with graphene sheets. No dissociative apparent from the surface areas and H2 uptake that only a fraction of chemisorption of H2 was observed in the entire course of AIMD the fluoride ions in the samples are accessible to H2.
simulations. Our results suggest that the calculated average H2 In summary, we propose a novel class of “acceptor type” GICs, adsorption energy decreases as H2 loading increases. At high H2 which based on theoretical predictions and experimental evidence, can H2 repulsion is largely responsible for the decrease exhibit significantly higher isosteric heats of adsorption for H2 than of H2 adsorption energy. At lower H2 loadings, however, the simulation previously demonstrated for commonly available, porous carbon-based suggests that the average adsorption energy is substantially higher than materials. The unusually strong interaction with H2 arises from the those observed in most porous carbons.
semi-ionic nature of the C-F bonds. Although high H2 storage capacity(>4 wt %) at near-ambient temperatures may not be feasible due todiminished heats of adsorption at very high H2 densities, enhancedstorage properties can be envisaged by doping the graphitic host withappropriate species (e.g., nitrogen) to promote higher levels of chargetransfer from graphene to F- anions. Synthetic strategies for increasingaccessibility of hydrogen to the intercalated anions are also underdevelopment.
Acknowledgment. The authors gratefully acknowledge funding
for this work provided by the U.S. DOE’s Office of Energy Efficiencyand Renewable Energy via the Hydrogen Sorption Center of Excellence(Contract DE-FC-05GO15074).
Note Added after ASAP Publication. Reference numbering was
Supporting Information Available: Computational and experimental
Figure 2. Hydrogen isotherms measured on C22F0.2(BF4)0.8 at 273, 298,
details and the MD trajectory for 12 H2 molecules in the partially fluorinated and 313 K and the derived isosteric heat of adsorption.
GIC lattice in AVI format. This material is available free of charge via To ascertain if partially fluorinated graphites are capable of the Internet at
adsorbing H2, we synthesized a number of first- and second-stage References
fluoride GIC samples and subsequently measured H2 isotherms andderived the isosteric heats of adsorption. Graphite fluoroborates, C (1) Schlapbach, L.; Zu¨ttel, A. Nature 2005, 434, 353.
(2) Grochala, W.; Edwards, P. P. Chem. ReV. 2004, 104, 1283.
were synthesized in a manner similar to that of previous reports13 by (3) Kubas, G. J. Chem. ReV. 2007, 107, 4152.
exposing crystalline graphite powder (Timrex SFG6, dried at 900 °C (4) (a) Cheng, H.; Pez, G. P.; Kern, G.; Kresse, G.; Hafner, J. J. Phys. Chem. 2001, 105, 736. (b) Watanabe, K.; Soma, M.; Onishi, T.; Tamaru, K. Nature
under argon) to a mixture of F2 and BF3 at room temperature. CxBF4 1971, 233, 160.
was then heated to 150 °C under vacuum, partially removing BF (5) Nyulasi, B.; Kovacs, A. Chem. Phys. Lett. 2006, 426, 26.
(6) Trewin, A.; Darling, G. R.; Cooper, A. I. New. J. Chem. 2008, 32, 17.
the lattice to form CxF(BF4)y.14 The partial decomposition of the CxBF4 (7) Sweany, R. L.; Ogden, J. S. Inorg. Chem. 1997, 36, 2523.
was designed to yield a mixed GIC which contains both naked fluoride (8) Yang, C.; Wang, X.; Omary, M. A. J. Am. Chem. Soc. 2007, 129, 15454.
(9) Watanabe, K.; Soma, M.; Onishi, T.; Tamaru, K. Nature 1971, 233, 160.
anions and residual BF4 which could function as a “spacer” to sustain (10) (a) Watanabe, N.; Nakajima, T.; Touhara, H. Graphite Fluorides; Elsevier: adequate interlayer spacing for the adsorption of H Amsterdam, 1988. (b) Fluorine-Carbon and Fluoride-Carbon Materials; Nakajima, T., Ed.; Marcel Dekker: New York, 1995.
isotherms on a number of CxFy(BF4)1-y (x ) 8-26, y ) 0.1-0.7) (11) Perdew, J.; Zunger, A. Phys. ReV. B 1981, 23, 5048.
samples were performed at pressures up to 1500 psia using differential (12) Nose´, S. J. Chem. Phys. 1984, 81, 511.
(13) (a) Rosenthal, G. L.; Mallouk, T. E.; Bartlett, N. Synth. Met. 1984, 9, 433.
pressure volumetric adsorption.15 The isosteric heat of adsorption (heat (b) Brusilovsky, D.; Selig, H.; Vaknin, D.; Ohana, I.; Davidov, D. Synth. Met. 1988, 23, 377.
2 coverage) revealed that partially fluorinated (14) Nikonorov, Y. I. Kinetika i Kataliz 1979, 20, 1598.
graphite can adsorb hydrogen at near-ambient temperatures with an (15) Zielinski, J. M.; Coe, C. G.; Nickel, R. J.; Romeo, A. M.; Cooper, A. C.; enthalpy as large as ca. -12 kJ/mol of H2 (Figure 2).
Pez, G. P. Adsorption 2007, 13, 1.
While this heat of adsorption is lower than what is predicted by the (16) Pace, E. L.; Siebert, A. R. J. Phys. Chem. 1959, 63, 1398.
(17) Benard, P.; Chahine, R. Langmuir 2001, 17, 1950.
MD simulations performed at low H2 loadings, the average enthalpy (18) (a) Dinca, M.; Dailly, A.; Liu, Y.; Brown, C. M.; Neumann, D. A.; Long, J. R.
is higher than those reported for nonintercalated carbon materials such J. Am. Chem. Soc. 2006, 128, 16876. (b) Ma, S.; Sun, D.; Ambrogio, M.;
Fillinger, J. A.; Parkin, S.; Zhou, H.-C. J. Am. Chem. Soc. 2007, 129, 1858.
as graphite16 (ca. -4 kJ/mol H2 at 20 K and H2 coverage of <0.9 (19) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, mmol/g) or activated carbon17 [-(6.5-5.0) kJ/mol H M. R.; Singh, D. J.; Fiolhais, C. Phys. ReV. B 1992, 46, 6671.
and H2 coverage of 0-12 mmol/g]. The measured H2 storage capacity J. AM. CHEM. SOC. 9 VOL. 131, NO. 49, 2009


Microsoft word - innogen working paper 14 - final.doc

Therapeutic advance of biopharmaceuticals . 6 Table 1. Prescrire definitions of the evaluation categories . 7 Table 2. Prescrire evaluations of the therapeutic value of biopharmaceuticals and all other drugs (Jan 1986 – June 2004) . 9 Table 3. Prescrire evaluations of biopharmaceutical indications over time .10 Drug share and prevalence rates for biopharmaceuticals .11 The social benefi

Microsoft word - allgemein_1 .doc

Verein für medizinische Qualitätskontrolle Association pour le contrôle de Qualité médical Associazione per il controllo di qualità medico Kommentar zum Ringversuch 2012-1 Allgemeine Hinweise Sie finden sämtliche wichtigen Informationen, ausführliche Berichte sowie Anleitungen auf H3 – Differentialblutbild Ausstrich H3-A stammt von einer gesunden Mitarbeiterin. Ausstric

Copyright ©2018 Drugstore Pdf Search