Search

Biochar (BC) boasts diverse environmental applications. However, its potential for environmental biomonitoring has, surprisingly, remained largely unexplored. This study presents a preliminary analysis of BC's potential as a biomonitor for the environmental availability of ionic Cd, utilizing the lichen Evernia prunastri (L.) Ach. as a reference organism. For this purpose, the lichen E. prunastri and two types of wood-derived biochar, biochar 1 (BC1) and biochar 2 (BC2), obtained from two anonymous producers, were investigated for their ability to accumulate, or sequester and subsequently release, Cd when exposed to Cd-depleted conditions. Samples of lichen and biochar (fractions between 2 and 4 mm) were soaked for 1 h in a solution containing deionized water (control), 10 µM, and 100 µM Cd 2+ (accumulation phase). Then, 50% of the treated samples were soaked for 24 h in deionized water (depuration phase). The lichen showed a very good ability to adsorb ionic Cd, higher than the two biochar samples (more than 46.5%), and a weak ability to release the metal (ca. 6%). As compared to the lichen, BC2 showed a lower capacity for Cd accumulation (-48%) and release (ca. 3%). BC1, on the other hand, showed a slightly higher Cd accumulation capacity than BC2 (+3.6%), but a release capacity similar to that of the lichen (ca. 5%). The surface area and the cation exchange capacity of the organism and the tested materials seem to play a key role in their ability to accumulate and sequester Cd, respectively. This study suggests the potential use of BC as a (bio)monitor for the presence of PTEs in atmospheric depositions and, perhaps, water bodies.

The molecular Pt nanocluster [Pt 27 (CO) 31 ] 4- ( 1 4- ) was obtained by thermal decomposition of [Pt 15 (CO) 30 ] 2- in tetrahydrofuran under a H 2 atmosphere. The reaction of 1 4- with increasing amounts of HBF 4 · Et 2 O afforded the previously reported [Pt 26 (CO) 32 ] 2- ( 3 2- ) and [Pt 26 (CO) 32 ] - ( 3 - ). The new nanocluster 1 4- was characterized by IR and UV-visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy. The cluster displays a cubic-close-packed Pt 27 framework generated by the overlapping of four ABCA layers, composed of 3, 7, 11, and 6 atoms, respectively, that encapsulates a fully interstitial Pt 4 tetrahedron. One Pt atom is missing within layer 3, and this defect (vacancy) generates local deformations within layers 2 and 3. These local deformations tend to repair the defect (missing atom) and increase the number of Pt-Pt bonding contacts, minimizing the total energy. The cluster 1 4- is perfectly diamagnetic and displays a rich electrochemical behavior. Indeed, six different oxidation states have been characterized by IR SEC, unraveling the series of 1 n - ( n = 3-8) isostructural nanoclusters. Computational studies have been carried out to further support the interpretation of the experimental data.

Optical excitation at terahertz frequencies has emerged as an effective means to dynamically manipulate complex materials. In the molecular solid K 3 C 60 , short mid-infrared pulses transform the high-temperature metal into a non-equilibrium state with the optical properties of a superconductor. Here we tune this effect with hydrostatic pressure and find that the superconducting-like features gradually disappear at around 0.3 GPa. Reduction with pressure underscores the similarity with the equilibrium superconducting phase of K 3 C 60 , in which a larger electronic bandwidth induced by pressure is also detrimental for pairing. Crucially, our observation excludes alternative interpretations based on a high-mobility metallic phase. The pressure dependence also suggests that transient, incipient superconductivity occurs far above the 150 K hypothesised previously, and rather extends all the way to room temperature.

Single-walled carbon nanotubes (SWCNTs) possessing a confined inner space protected by chemically resistant shells are promising for delivery, storage, and desorption of various compounds, as well as carrying out specific reactions. Here, we show that SWCNTs interact with molten mercury dichloride (HgCl 2 ) and guide its transformation into dimercury dichloride (Hg 2 Cl 2 ) in the cavity. The chemical state of host SWCNTs remains almost unchanged except for a small p-doping from the guest Hg 2 Cl 2 nanocrystals. The density functional theory calculations reveal that the encapsulated HgCl 2 molecules become negatively charged and start interacting via chlorine bridges when local concentration increases. This reduces the bonding strength in HgCl 2 , which facilitates removal of chlorine, finally leading to formation of Hg 2 Cl 2 species. The present work demonstrates that SWCNTs not only serve as a template for growing nanocrystals but also behave as an electron-transfer catalyst in the spatially confined redox reaction by donation of electron density for temporary use by the guests.

Through the substitution of Li with Na in Li 6 C 60 , we synthesized a series of mixed alkali cluster intercalated fullerides, Na x Li 6-x C 60 . These compounds share lattices of Na 6 C 60 and Li 6 C 60 with a cubic parameter linearly dependent on x. H 2 absorption and desorption were studied by means of charge/discharge kinetic measurements and coupled calorimetric-manometric evaluation. By varying the stoichiometry, we found the best compromise among the absorption rate, temperature and amount of hydrogen for x = 0.5 and 1. Small concentrations of Na substituted to Li significantly lower the absorption temperature of Li 6 C 60 , improving the hydrogenation capacity, the kinetics, and the dehydrogenation enthalpy, the latter being 43.8 kJ mol -1 H 2 for x = 1. This study moves further toward the utilization of intercalated fullerides for hydrogen storage applications.

We present a detailed NMR study of the insulator-to-metal transition induced by an applied pressure p in the A15 phase of Cs_{3}C_{60}. We evidence that the insulating antiferromagnetic (AFM) and superconducting (SC) phases coexist only in a narrow p range. At fixed p, in the metallic state above the SC transition T_{c}, the ^{133}Cs and ^{13}C NMR spin-lattice relaxation data are seemingly governed by a pseudogaplike feature. We prove that this feature, also seen in the ^{133}Cs NMR shift data, is rather a signature of the Mott transition which broadens and smears out progressively for increasing (p,T). The analysis of the variation of the quadrupole splitting ν_{Q} of the ^{133}Cs NMR spectrum precludes any cell symmetry change at the Mott transition and only monitors a weak variation of the lattice parameter. These results open an opportunity to consider theoretically the Mott transition in a multiorbital three-dimensional system well beyond its critical point.

In the substantia nigra of human brain, neuromelanin (NM) released by degenerating neurons can activate microglia with consequent neurodegeneration, typical of Parkinson's disease (PD). Synthetic analogues of NM were prepared to develop a PD model reproducing the neuropathological conditions of the disease. Soluble melanin-protein conjugates were obtained by melanization of fibrillated β-lactoglobulin (fLG). The melanic portion of the conjugates contains either eumelanic (EufLG) or mixed eumelanic/pheomelanic composition (PheofLG), the latter better simulating natural NMs. In addition, the conjugates can be loaded with controlled amounts of iron. Upon melanization, PheofLG-Fe conjugates maintain the amyloid cross-β protein core as the only structurally organized element, similarly to human NMs. The similarity in composition and structural organization with the natural pigment is reflected by the ability of synthetic NMs to activate microglia, showing potential of the novel conjugates to model NM induced neuroinflammation. Thus, synthetic NM/microglia constitute a new model to develop anti-Parkinson drugs.

Two chemically synthesized defective graphene materials with distinctly contrasting extended structures and surface chemistry are used to prepare sodium-ion battery electrodes. The difference in electrode performance between the chemically prepared graphene materials is qualified based on correlations with intrinsic structural and chemical dissimilarities. The overall effects of the materials' physical and chemical discrepancies are quantified by measuring the electrode capacities after repeated charge/discharge cycles. Solvothermal synthesized graphene (STSG) electrodes produce capacities of 92 mAh/g in sodium-ion batteries after 50 cycles at 10 mA/g, while thermally exfoliated graphite oxide (TEGO) electrodes produce capacities of 248 mAh/g after 50 cycles at 100 mA/g. Solid-state 23 Na nuclear magnetic resonance spectroscopy is employed to locally probe distinct sodium environments on and between the surface of the graphene layers after charge/discharge cycles that are responsible for the variations in electrode capacities. Multiple distinct sodium environments of which at least 3 are mobile during the charge-discharge cycle are found in both cases, but the majority of Na is predominantly located in an immobile site, assigned to the solid electrolyte interface (SEI) layer. Mechanisms of sodium insertion and extraction on and between the defective graphene surfaces are proposed and discussed in relation to electrode performance. This work provides a direct account of the chemical and structural environments on the surface of graphene that govern the feasibility of graphene materials for use as sodium-ion battery electrodes.

Understanding the mobility of H at the surface of carbon nanostructures is one of the essential ingredients for a deep comprehension of the catalytic formation of H 2 in interstellar clouds. In this paper, we combine neutron vibrational spectroscopy with DFT molecular dynamics simulations to study the local environment of H structures chemisorbed at the surface of disordered graphene sheets. At 5 K, the ground state is composed of large clusters of hydrogen chemisorbed at sp 2 carbon sites, on the edges and in voids of the graphene sheets. At temperatures of ∼300 K, a high degree of dispersion of the clusters is observed, involving the breaking and reforming of covalent bonds which, at low temperatures, is mediated by incoherent tunnelling of hydrogen.

The non-equilibrium control of emergent phenomena in solids is an important research frontier, encompassing effects such as the optical enhancement of superconductivity. Nonlinear excitation of certain phonons in bilayer copper oxides was recently shown to induce superconducting-like optical properties at temperatures far greater than the superconducting transition temperature, Tc (refs 4-6). This effect was accompanied by the disruption of competing charge-density-wave correlations, which explained some but not all of the experimental results. Here we report a similar phenomenon in a very different compound, K3C60. By exciting metallic K3C60 with mid-infrared optical pulses, we induce a large increase in carrier mobility, accompanied by the opening of a gap in the optical conductivity. These same signatures are observed at equilibrium when cooling metallic K3C60 below Tc (20 kelvin). Although optical techniques alone cannot unequivocally identify non-equilibrium high-temperature superconductivity, we propose this as a possible explanation of our results.

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Cs3C60 is an antiferromagnetic insulator that under pressure (P) becomes metallic and superconducting below Tc = 38 K. The superconducting dome present in the T - P phase diagram close to a magnetic state reminds what found in superconducting cuprates and pnictides, strongly suggesting that superconductivity is not of the conventional Bardeen-Cooper-Schrieffer (BCS) type We investigate the insulator to metal transition induced by pressure in Cs3C60 by means of infrared spectroscopy supplemented by Dynamical Mean-Field Theory calculations. The insulating compound is driven towards a metallic-like behaviour, while strong correlations survive in the investigated pressure range. The metallization process is accompanied by an enhancement of the Jahn-Teller effect. This shows that electronic correlations are crucial in determining the insulating behaviour at ambient pressure and the bad metallic nature for increasing pressure. On the other hand, the relevance of the Jahn-Teller coupling in the metallic state confirms that phonon coupling survives in the presence of strong correlations.

The new bimetallic [HCo15Pd9C3(CO)38](2-) tri-carbide carbonyl cluster has been obtained from the reaction of [H2Co20Pd16C4(CO)48](4-) with an excess of acid in CH2Cl2 solution. The mono-hydride di-anion can be reversibly protonated and deprotonated by means of acid-base reactions leading to closely related [H(3-n)Co15Pd9C3(CO)38](n-) (n = 0-3) clusters. The crystal structures of the three anionic and the neutral clusters have been determined as their H3Co15Pd9C3(CO)38·2thf, [NEt4][H2Co15Pd9C3(CO)38]·0.5C6H14, [NMe3(CH2Ph)]2[HCo15Pd9C3(CO)38]·C6H14 and [NEt4]3[Co15Pd9C3(CO)38]·thf salts. They are composed of a Pd9(μ3-CO)2 core stabilised by three Co5C(CO)12 organometallic fragments. The poly-hydride nature of these clusters has been indirectly inferred via chemical, electrochemical and magnetic measurements. Besides, cyclic voltammetry shows that the [H(3-n)Co15Pd9C3(CO)38](n-) (n = 1-3) anions are multivalent, since they undergo two or three reversible oxidations. SQUID measurements of [HCo15Pd9C3(CO)38](2-) indicate that this even electron cluster is paramagnetic with two unpaired electrons, giving further support to its hydride nature. Finally, structural studies show that the Pd9 core of [H(3-n)Co15Pd9C3(CO)38](n-) (n = 0,1) is a tri-capped octahedron, which becomes a tri-capped trigonal prism in the more charged [H(3-n)Co15Pd9C3(CO)38](n-) (n = 2,3) anions. Such a significant structural rearrangement of the metal core of a large carbonyl cluster upon protonation-deprotonation reactions is unprecedented in cluster chemistry, and suggests that interstitial hydrides may have relevant stereochemical effects even in large carbonyl clusters.

Former extensive studies of superconductivity in the A3C60 compounds, where A is an alkali metal, have led one to consider that Bardeen-Cooper-Schrieffer electron-phonon pairing prevails in those compounds, though the incidence of electronic Coulomb repulsion has been highly debated. The discovery of two isomeric fulleride compounds Cs3C60 which exhibit a transition with pressure from a Mott insulator (MI) to a superconducting (SC) state clearly reopens that question. Using pressure (p) as a single control parameter of the C60 balls lattice spacing, one can now study the progressive evolution of the SC properties when the electronic correlations are increased towards the critical pressure p(c) of the Mott transition. We have used 13C and 133Cs NMR measurements on the cubic phase A15-Cs3C60 just above p(c)=5.0(3) kbar, where the SC transition temperature Tc displays a dome shape with decreasing cell volume. From the T dependence below T(c) of the nuclear spin lattice relaxation rate (T1)(-1) we determine the electronic excitations in the SC state, that is 2Δ, the gap value. The latter is found to be largely enhanced with respect to the Bardeen-Cooper-Schrieffer value established in the case of dense A3C60 compounds. It even increases slightly with decreasing p towards p(c), where T(c) decreases on the SC dome, so that 2Δ/k(B)T(c) increases regularly upon approaching the Mott transition. These results bring clear evidence that the increasing correlations near the Mott transition are not significantly detrimental to superconductivity. They rather suggest that repulsive electron interactions might even reinforce elecron-phonon superconductivity, being then partly responsible for the large T(c) values, as proposed by theoretical models taking the electronic correlations as a key ingredient.

Here, 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 CH(2)) 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.

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 p{c} and temperatures T{c}. 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.

The reaction of [Co(6)C(CO)(15)](2-) with 2 equiv of PtCl(2)(Et(2)S)(2) affords the new heterobimetallic [Co(8)Pt(4)C(2)(CO)(24)](2-), [1](2-), carbonyl cluster. [1](2-) undergoes reversible chemical and electrochemical oxidation and reduction processes disclosing a complete series of [1](n-) (n = 1-4) clusters. The mono- and dianion of [1](n-) have been isolated as their tetra-substituted ammonium salts and fully characterized by means of IR, (13)C NMR, ESI-MS, and X-ray crystallography. Variable-temperature (VT) solid-state EPR studies on pure crystalline samples indicate that both [1](2-) and [1](-*) are paramagnetic, due to a doublet state of the latter and a triplet state of [1](2-). This conclusion is supported by SQUID measurements on the same crystalline sample of [1](2-). The present study indisputably demonstrates that even-electron transition metal carbonyl clusters (TMCC) can be magnetic.

We report here 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, AsF(5). 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 C(60)(AsF(6))(2), indicates that the highly reactive C(60)(2+) 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-T(c) superconductivity and magnetism, expected in a hole-doped C(60) 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.

We report on the extraordinary superionic conductivity in the fulleride polymer Li4C60, a crystalline material with no disorder. 7Li, NMR, and dc frequency dependent conductivity show uncorrelated ionic hopping across small energy barriers (DeltaE_{a} approximately 200 meV) and an ionic conductivity of 10;{-2} S/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.

All known fullerene polymers have interfullerene connections via either [2 + 2] cycloaddition or single C-C bonds. The high-resolution synchrotron X-ray powder diffraction technique was employed here to determine the crystal structure of the Li4C60 fulleride. We find that the ground state of Li4C60 is a two-dimensional polymer with monoclinic crystal symmetry and an unprecedented architecture, combining both the [2 + 2] cycloaddition and the single C-C bridging motifs. The small size of the Li+ cations is crucial in stabilizing the resulting tightly packed polymeric structure.