Reversible hydrogen absorption in sodium intercalated fullerenes

The hydrogen absorption of sodium intercalated fullerenes was determined and
compared to pure fullerenes C60. Up to 3.5 mass% hydrogen can reversibly be absorbed in NaxC60 at 200 C and a hydrogen pressure of 200 bar. The absorbed amount of hydrogen is significantly higher than for the case when only the sodium would be hydrogenated. At 200 bar the onset of hydrogen absorption is observed at 150 C. At a pressure of 1 bar hydrogen the major desorption starts at 250 C and is completed at 300 C. This absorption and desorption temperatures are significantly reduced compared to pure C60, either due to a catalytic reaction of hydrogen on sodium or due to the negatively charged C60. The hydrogen ab/desorption is accompanied by a partial de/reintercalation of sodium. A minor part of the hydrogen is ionically bonded in NaH and the major part is covalently bonded in C60Hx. The sample can be fully dehydrogenated and no NaH is left after desorption. In contrast to C60, where the fullerene cages for high hydrogen loadings are destroyed during the sorption process, the NaxC60 sample stays intact.


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Muons Probe Strong Hydrogen Interactions with Defective Graphene

We present the first muon spectroscopy investigation of graphene, focused on chemically produced, gram-scale samples, appropriate to the large muon penetration depth. We have observed an evident muon spin precession, usually the fingerprint of magnetic order, but here demonstrated to originate from muon–hydrogen nuclear dipolar interactions. This is attributed to the formation of CHMu (analogous to CH2) groups, stable up to 1250 K where the signal still persists. The relatively large signal amplitude demonstrates an extraordinary hydrogen capture cross section of CH units. These results also rule out the formation of ferromagnetic or antiferromagnetic order in chemically synthesized graphene samples.

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NMR Study of the Mott Transitions to Superconductivity in the Two Cs3C60 Phases

We report a NMR and magnetometry study on the expanded intercalated fulleride Cs3C60 in both its A15 and face centered cubic structures. NMR allowed us to evidence that both exhibit a first-order Mott transition to a superconducting state, occurring at distinct critical pressures pc and temperatures Tc. Though the ground state magnetism of the Mott phases differs, their high T paramagnetic and superconducting properties are found similar, and the phase diagrams versus unit volume per C60 are superimposed. Thus, as expected for a strongly correlated system, the interball distance is the relevant parameter driving the electronic behavior and quantum transitions of these systems.

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Fullerenium Salts: A New Class of C60-Based Compounds

We report on the preparation and characterization of a fullerenium salt in the solid state, where the fullerene is in the 2+ oxidized state. To succeed in this long-standing challenge, we exploit the oxidizing power of one of the strongest Lewis acids, AsF5. The weak nucleophilic character of its conjugate base is essential in stabilizing the fullerene dication in a crystal lattice. High-resolution structural analysis of this compound, with the formula C60(AsF6)2, indicates that the highly reactive C602+ units are arranged according to a novel 1D “zigzag” polymer structure. The molecules are connected by an alternating sequence of four-membered carbon rings ([2 + 2] cycloaddition) and single C−C bonds. The long awaited high-Tc superconductivity and magnetism, expected in a hole-doped C60 compound, are replaced instead by a semiconducting behavior, quite probably originating from the reduced crystal and molecular symmetry upon polymerization. The small value of the energy gap (approximately 70 meV) suggests, nevertheless, the proximity of a metallic phase.

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Superionic Conductivity in the Li4C60 Fulleride Polymer

We report on the extraordinary superionic conductivity in the fulleride polymer Li4C60 , a crystalline material with no disorder. 7Li , NMR, and dc/ac conductivity show uncorrelated ionic hopping across small energy barriers (ΔEa200meV ) and an ionic conductivity of 102S/cm at room temperature, higher than in “standard” ionic conductors. Ab initio calculations of the molecular structure find intrinsic unoccupied interstitial sites that can be filled by Li+ cations in stoichiometric Li4C60 even at low temperatures. The low energy required for the occupation of these sites allows a sizable Li+ diffusion above 130 K. The results suggest novel application of lithium intercalated fullerides as electrodes in Li ions batteries.

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