The melting transition of methane adsorbed in nanopores has been studied and compared in two types of structures: carbon slits pores and SURMOF square shaped channels. We show that the nano-confinement not only modifies the temperatures of phase transformation but also induces strong space heterogeneity of the adsorbate. We emphasize the role of the structural heterogeneity on the mechanism of melting: in nanometric pores, each adsorbed layer exhibits different mechanism of structural transformations and the notion of a unique transition temperature is not well defined.

We present the results of extensive fully atomistic molecular dynamics (MD) simulations of tetracosane (C24H50) bilayer and trilayer systems adsorbed onto the basal plane of graphite. At low temperature, both layers of the bilayer exist in well-defined solid phases. With increasing temperature, the system exhibits separated smectic phases that eventually lead to melting. During this process, we observed a strong interlayer translational correlation and mobility between layers; however, the upper layer presents more intra- (chain) and intermolecular disorder because of a lack of confinement and a greater distance to the graphite substrate. Simulations of the perpendicular trilayer patch show that gauche defects provide the main mechanism for spreading of the bottom and outer perimeter of the patch in the solid, leading to the ultimate collapse of the patch with increasing temperature and formation of a flat (parallel) trilayer that melts at a higher temperature than the bilayer structure. The wide variety of structural order parameters, thermodynamic functions, and probability distributions we employed provide a clear picture of the roles of gauche defects, confinement, and interlayer correlation in the phases and phase transitions exhibited by these confined organic layers.

The efficient storage and transportation of natural gas is one of the most important enabling technologies for use in energy applications. Adsorption in porous systems, which will allow the transportation of high-density fuel under low pressure, is one of the possible solutions. We present and discuss extensive grand canonical Monte Carlo (GCMC) simulation results of the adsorption of methane into slit-shaped graphitic pores of various widths (between 7 angstrom and 50 angstrom), and at pressures P between 0 bar and 360 bar. Our results shed light on the dependence of film structure on pore width and pressure. For large widths, we observe multi-layer adsorption at supercritical conditions, with excess amounts even at large distances from the pore walls originating from the attractive interaction exerted by a very high-density film in the first layer. We are also able to successfully model the experimental adsorption isotherms of heterogeneous activated carbon samples by means of an ensemble average of the pore widths, based exclusively on the pore-size distributions (PSD) calculated from subcritical nitrogen adsorption isotherms. Finally, we propose a new formula, based on the PSD ensemble averages, to calculate the isosteric heat of adsorption of heterogeneous systems from singlepore-width calculations. The methods proposed here will contribute to the rational design and optimization of future adsorption-based storage tanks.

The role of fundamental characteristics of porous systems (binding energy, specific surface area and multilayer adsorption) in designing an efficient hydrogen adsorbent is discussed. We analyze why the amount of hydrogen adsorbed in all known materials is much lower than required for mobile applications and what are possible strategies to increase it. Further we report new ab initio calculations demonstrating possible ways of chemical modification of graphene fragments which can lead to the substantial increase of hydrogen binding to the graphene-based surface. Such Open Carbon Frameworks, substituted and functionalized at the fragments' edge may theoretically adsorb, at ambient temperature and relatively low pressure (60-100 bar), the amount of hydrogen necessary for mobile applications.

Graphene, known as one carbon layer material, holds attractive properties due to its hexagonal lattice, also called honeycomb structure. Since the seminal work on mechanically exfoliated few layer graphene, more growth processes were explored: Chemical Vapor Deposition (CVD) on metals or on silicon carbide (SiC); chemical reduction of graphene oxides and SiC sublimation. In contrast to the other graphene growth techniques, thermal decomposition of SiC provides wafer-scale homogeneous graphene spontaneously forming on semi-insulating substrate. SiC sublimation is the most promising option to achieve the transfer free and wafer-scale graphene. Furthermore, graphene/SiC is compatible with lithography techniques for further applications; thereby epitaxial graphene on SiC is a potential candidate for nanoelectronics. Until now, monolayer graphene growth by SiC sublimation at a pressure closed to the atmospheric pressure (around 900 mbar) and at high temperature (>1650°C) is well known . However, to obtain films with different and controlled characteristics such as the number of graphene layers or the type of doping by controlling the growth parameters remains challenging. We will present the initial growth stages from buffer layer to monolayer graphene on SiC (0001) as a function of the temperature at low pressure (10 mbar). A reproducible synthesis of low p-type doped monolayer graphene was optimized (few 10^11 cm-2). The p-type doping are obtained here on the bare samples without any post-growth process such as lithography. A prototypal HTA-100 furnace developed by Annealsys Company has allowed the synthesis of these original samples. All the samples were characterized by Raman spectroscopy and Atomic Force Microscopy (AFM). In addition, transport measurements (at room temperature and low temperature with high magnetic field) were carried out in the case of continuous monolayer graphene films showing especially characteristics of Quantum Hall Effect.

Liquid phase encapsulation of α-sexithiophene (6T) molecules inside individualized single-walled carbon nanotubes (SWCNTs) is investigated using Ramanimaging and spectroscopy. By taking advantage of the strong Raman response of this system, we probe the encapsulation isotherms at 30°C and 115°C using a statistical ensemble of SWCNT deposited on a Si/SiO2 substrate. Two distinct and sequential stages ofencapsulation are observed: Stage 1 is a one-dimensional (1D) aggregation of 6T alignedhead-to-tail inside the nanotube and stage 2 proceeds with the assembly of a second row, giving pairs of aligned 6Ts stacked together side-by-side. The experimental data are fitted using both Langmuir (type VI) and Ising models, in which the single-aggregate (stage 1) forms spontaneously whereas the pair-aggregate (stage 2) is endothermic in toluene with formation enthalpy of 8Hpair = 260±20 meV. Tunable Raman spectroscopy for each stage reveals a bathochromic shift of the molecular resonance of the pair-aggregate, which is consistent with strong inter-molecular coupling and suggestive of J-type aggregation. This quantitative Raman approach is sensitive to roughly 10 molecules per nanotube andprovides direct evidence of molecular entry from the nanotube ends. These insights into the encapsulation process guide the preparation of well-defined 1D molecular crystals having tailored optical properties.