EPR, ENDOR, and HYSCORE Study of the Structure and the Stability of Vanadyl−Porphyrin Complexes Encapsulated in Silica: Potential Paramagnetic Biomarkers for the Origin of Life
Gourier*†, Olivier Delpoux†, Audrey Bonduelle†, Laurent Binet†, Ilaria Ciofini‡ and Herv Vezin§
J. Phys. Chem. B, 2010, 114 (10), pp 3714–3725
Abstract: The possibility of using vanadyl ions as paramagnetic biomarkers for the identification of traces of primitive life fossilized in silica rocks is studied by cw-EPR, ENDOR, HYSCORE, and DFT calculations. It is well-known that porphyrins, which are common to all living organisms, form vanadyl−porphyrin complexes in sediments deposited in oceans. However, the stability of these complexes over a very long time (more than 3 billion years) is not known. By encapsulating vanadyl−porphyrin complexes in silica synthesized by a sol−gel method to mimic SiO2 sediments, we studied the structure and stability of these complexes upon step heating treatments by monitoring the evolution of the g factor and of the hyperfine interactions with 51V, 1H, 14N, 13C, and 29Si nuclei. It is found that vanadyl−porphyrin complexes are progressively transformed into oxygenated vanadyl complexes by transfer of the VO2+ ion from the porphyrin ring to the mineral matrix. The organic component is transformed into carbonaceous matter which contains paramagnetic centers (IOM• centers). To test the validity of this approach, we studied by EPR a 3490 million years old chert (polycrystalline SiO2 rock) containing some of the oldest putative traces of life. This rock contains oxygenated vanadyl complexes and IOM• centers very similar to those found in the synthetic analogues.
Confinement of NaAlH4 in Nanoporous Carbon: Impact on H2 Release, Reversibility, and Thermodynamics
Jinbao Gao†, Philipp Adelhelm†, Margriet H. W. Verkuijlen‡, Carine Rongeat§, Monika Herrich§, P. Jan M. van Bentum‡, Oliver Gutfleisch§, Arno P. M. Kentgens‡, Krijn P. de Jong† and Petra E. de Jongh*†
J. Phys. Chem. C, 2010, 114 (10), pp 4675–4682
Abstract: Metal hydrides are likely candidates for the solid state storage of hydrogen. NaAlH4 is the only complex metal hydride identified so far that combines favorable thermodynamics with a reasonable hydrogen storage capacity (5.5 wt %) when decomposing in two steps to NaH, Al, and H2. The slow kinetics and poor reversibility of the hydrogen desorption can be combatted by the addition of a Ti-based catalyst. In an alternative approach we studied the influence of a reduced NaAlH4 particle size and the presence of a carbon support. We focused on NaAlH4/porous carbon nanocomposites prepared by melt infiltration. The NaAlH4 was confined in the mainly 2−3 nm pores of the carbon, resulting in a lack of long-range order in the NaAlH4 structure. The hydrogen release profile was modified by contact with the carbon; even for 10 nm NaAlH4 on a nonporous carbon material the decomposition of NaAlH4 to NaH, Al, and H2 now led to hydrogen release in a single step. This was a kinetic effect, with the temperature at which the hydrogen was released depending on the NaAlH4 feature size. However, confinement in a nanoporous carbon material was essential to not only achieve low H2 release temperatures, but also rehydrogenation at mild conditions (e.g., 24 bar H2 at 150 °C). Not only had the kinetics of hydrogen sorption improved, but the thermodynamics had also changed. When hydrogenating at conditions at which Na3AlH6 would be expected to be the stable phase (e.g., 40 bar H2 at 160 °C), instead nanoconfined NaAlH4 was formed, indicating a shift of the NaAlH4↔Na3AlH6 thermodynamic equilibrium in these nanocomposites compared to bulk materials.
Solid-State NMR Studies of the Local Structure of NaAlH4/C Nanocomposites at Different Stages of Hydrogen Desorption and Rehydrogenation
Margriet H. W. Verkuijlen†, Jinbao Gao‡, Philipp Adelhelm‡, P. Jan M. van Bentum*†, Petra E. de Jongh‡ and Arno P. M. Kentgens*†
J. Phys. Chem. C, 2010, 114 (10), pp 4683–4692
Abstract: Structural properties of NaAlH4/C nanocomposites were studied using 23Na and 27Al solid-state NMR. The samples were synthesized by melt infiltration of a highly porous carbon support, with typical pore sizes of 2−3 nm. Physical mixtures of high surface carbon with alanates in different stages of hydrogen desorption show somewhat broadened resonances and a small negative chemical shift compared to pure alanates. This is most likely caused by a susceptibility effect of the carbon support material, which shields and distorts the applied magnetic field. After melt infiltration, 23Na and 27Al spectra are broadened with a small downfield average shift, which is mainly caused by a chemical shift distribution and is explained by a larger disorder in the nanoconfined materials and a possible charge transfer to the carbon. Our measurements show that the local structure of the nanoconfined alanate is the similar to bulk alanate because a comparable chemical shift and average quadrupolar coupling constant is found. In contrast to bulk alanates, in partly desorbed nanocomposite samples no Na3AlH6 is detected. Together with a single release peak observed by dehydrogenation experiments, this points toward a desorption in one single step. 23Na spectra of completely desorbed NaAlH4/C and NaH/C nanocomposites confirm the formation of metallic sodium at lower temperatures than those observed for bulk alanates. The structural properties observed with solid-state NMR of the nanoconfined alanate are restored after a rehydrogenation cycle. This demonstrates that the dehydrogenation of the NaAlH4/C nanocomposite is reversible, even without a Ti-based catalyst.
Transferred Hyperfine Interaction between a Tetrahedral Transition Metal and Tetrahedral Lithium: Li6CoO4
Dany Carlier*, Michel Mntrier and Claude Delmas
J. Phys. Chem. C, 2010, 114 (10), pp 4749–4755
Abstract: Li6CoO4 presents an antifluorite-type structure, with both the Co and Li ions in tetrahedral oxygen coordination. 7Li MAS NMR shows remarkably different shifts (+885 and −232 ppm) for the two different crystallographic types of Li. In order to assign the signals and to understand the mechanisms whereby the electron spins on the e orbitals of Co2+ ions (e4 t23 electronic configuration) are transferred toward the two different types of Li with opposite polarization, we have carried out GGA and GGA+U calculations of the electronic structure using the VASP code. Spin density maps in selected planes of the structure reveal (as expected) that lobes of the t2 orbitals point toward the faces of the CoO4 tetrahedra and can thus overlap with the neighboring Li(2) through empty square pyramidal sites. As concerns Li(1), a mechanism is evidenced where the (filled) e orbitals of Co2+ are polarized by the electron spins in the t2 ones. These polarized e orbitals overlap with Li(1) through the common edge of the tetrahedra. The relative magnitude of the experimental shifts for the two types of Li are however not fully reproduced by the calculations, and the influence of the U parameter as well as of the pseudopotential method used is discussed.
A Combined Hydrogen Storage System of Mg(BH4)2−LiNH2 with Favorable Dehydrogenation
X. B. Yu*†‡, Y. H. Guo‡, D. L. Sun‡, Z. X. Yang§, A. Ranjbar†, Z. P. Guo†, H. K. Liu† and S. X. Dou†
J. Phys. Chem. C, 2010, 114 (10), pp 4733–4737
Abstract: The decomposition properties of Mg(BH4)2−LiNH2 mixtures were investigated. Apparent NH3 release appeared from 50 to 300 °C for the Mg(BH4)2−LiNH2 mixtures with mole ratios of 1:1.5, 1:2, and 1:3, while only hydrogen release was detected for the mixture with a mole ratio of 1:1. In the case of the Mg(BH4)2−LiNH2 (1:1) sample, the onset of the first-step dehydrogenation starts at 160 °C, with a weight loss of 7.2 wt % at 300 °C, which is improved significantly compared to the pure Mg(BH4)2 alone. From Kissinger’s method, the activation energy, Ea, for the first and second step dehydrogenation in Mg(BH4)2−LiNH2 (1:1) was estimated to be about 121.7 and 236.6 kJ mol−1, respectively. The improved dehydrogenation in the combined system may be ascribed to a combination reaction between [BH4] and [NH2], resulting in the formation of Li−Mg alloy and amorphous B−N compound.