The adequate choice of the interaction model is essential to reproduce qualitatively and estimate quantitatively the experimentally observed characteristics of materials or phenomena in computer simulations. Here we present the results of a benchmarking of density-functional theory calculations of rigid and flexible metal-organic frameworks (MOFs). The stability of these systems depends on the dispersion interactions. We compare the performance of two functionals, Perdew-Burke-Ernzerhof (PBE) and PBE designed for solids, with and without the dispersion corrections (D2 and TS), in reproducing the high-accuracy low-temperature X-ray and neutron diffraction data for both groups of MOFs. We focus our analysis on the key structural parameters: the lattice parameters, bond lengths, and angles. We show that the dispersion long range correction is essential to stabilize the structures and, in some cases, to converge the system to a geometry that is in line with the experimentally observed structure, especially for breathing MIL-53 structures or zeolitic imidazolate frameworks. We find that for all structures and all analyzed parameters, the D2-corrected PBE functional performs the best, except for bonds involving the metal ions; however, even for these bonds the difference between the experimentally observed and calculated lengths is small. Therefore, we recommend the use of the PBE-D2 functional in further numerical analyses of rigid and flexible nanoporous MOFs.

Aqueous dispersions of graphene-derived monolayers form liquid crystal at rather low concentrations due to the high aspect ratio of these flakes [1,2]. If graphene oxide dispersions are easily obtained in water, reduced graphene oxide necessitates the use of surfactants [3]. Preparing organized materials and thin films from these dispersions then requires a good control of the liquid crystal ordering during the deposition and the drying of the films.The flakes easily align at high shear [4,5], which has allowed us to complete previous optical characterizations of the various graphene layers (birefringence and linear dichroism). However at low shear or under small dispalcements, thin films often show peculiar patterns (such as the periodic textures shown in Fig.1). We have shown how to create and stabilize large-sized periodic textures. The patterns have been characterized under optical and electronic microscopies. Their stability can be explained by the competition between the anchoring field of the substrate and the presence of a yield stress resulting from the peculiar elastic and rheological properties of the graphene oxide liquid crystals. Our results also clarify why long-standing hypotheses on the presence of exotic phases [1] at large concentrations are present in the literature.References[1] Z. Xu, C. Gao Nat Commun., 2, 571 (2011).[2] C. Zakri et al., Phil. Trans. A, 371, 20120499 (2013).[3] C. Zamora et al, J. Phys. Chem. Lett. 3, 2425 (2012).[4] P. Poulin et al, Proc Natl Acad Sci USA, 113, 11088 (2016).[5] S-H Honga, T.Z. Shena and J. K. Songa, Liquid Crystals, 42, 261 (2015)

Thin and ultrathin metal coatings are increasingly required by the electronics and optics industries onall types of substrates. However, the adhesion of noble metals is very poor on non-metallic substrates like glass,other oxide materials and polymers. By contrast, CVD graphene has a strong adhesion energy (~0.31-0.45 J.m-2depending on the number of layers) on glass [1]. On the other hand, graphene oxide (GO) was recently shown topromote adhesion of ZnO nanoparticles and subsequent ZnO films on glass or silicon substrates [2].In this work we use GO/Au nanoparticles (NP) composite thin films as bifunctional materials to bothpromote adhesion on glass and assist the deposition of copper in electroless wet industrial coating processes. Wediscuss the influence of the NP density, surface treatment and deposition parameters on the homogeneity andadhesion of the GO/Au NP and copper layers.[1] S. P. Koenig, N. G. Boddeti, M. L. Dunn, and J. S. Bunch, 2011, Nat. Nano. 6, 543‑546[2] Q. Ma, X. Zhu, D. Zhang, and S. Liu, 2014, J. Mater. Chem. C 22, 8956‑8961

In this work, we explore the preparation and deposition of graphene oxide (GO)-metal (gold and palladium) nanoparticles (NPs) composites as thin films via wet routes. The properties of such films are examined, in view of Surface Enhanced Raman Spectroscopy (SERS) applications and as adhesion promoter thin films. It has been indeed shown that the encapsulation of metal NP within a few layers of graphene greatly improves the stability, reproducibility and sensitivity of SERS effect [1]. On the other hand, graphene oxide films decorated with metal nanoparticles are good non-etching adhesion promotors candidates for electroless deposition of metal thin films on non-metal substrates like glass or polymers [2, 3]. We discuss the preparation of the suspensions and the parameters (GO dispersion concentration, withdrawal speed and immersion time, functionalization of the substrates) which permit a good control of the deposition by dip-coating. The structure of the resulting thin films is characterized by Atomic Force Microscopy (AFM), Phase Shifting Interferometry (PSI) and Raman spectroscopy to determine the topography, thickness and homogeneity of the deposited layers. Their SERS and adhesion properties are then discussed.References[1] Y. Liu, Y. Hu, and J. Zhang, J. Phys. Chem. C, 2014, 1187, p. 8993‑ 8998.[2] S. P. Koenig, N. G. Boddeti, M. L. Dunn, and J. S. Bunch,2011, Nat. Nanotechnol.,6, p. 543‑ 546.[3] Q. Ma, X. Zhu, D. Zhang, and S. Liu, 2014, J. Mater. Chem. C,22, p. 8956‑ 8961.

We explore the preparation and use of graphene dispersions and graphene-nanoparticles composites viawet routes in order to create organized thin films (for passivation, adhesion and design of SERS substrates, seeFig.) At large concentrations, the liquid crystal ordering is an opportunity to spontaneously organize the materials.At lower concentrations, a special care has to be taken during the deposition of the thinnest films.In this work, we have focused on the design and the characterization of thin layers made of graphene oxide andgold nanoparticles (GO/AuNps) for their Surface Enhanced Raman Spectroscopy (SERS) properties. The objectivehere is to establish the main rules that control (during the deposition) the structure of the films and their resultingSERS properties. We have used various techniques such as dip-coating, spin coating with varying parameters, aswell as surface functionalization before deposition. The thin films have been characterized by AFM and theirperformance have been tested with Raman spectroscopy.

Graphene oxide dispersions are easily obtained in water. Due to the high aspect ratio of the flakes, liquid crystalsthen forms a nematic phase at moderate concentrations [1,2], which allows to design various composites withnanoparticles. Preparing organized materials and thin films from these dispersions however requires a good controlof the liquid crystal ordering during the deposition and the drying of the films.Here we have focused on mechanical instabilities that are frequently observed in thin graphene liquid crystallayers, when they are submitted to weak constraints. We have shown how to create and stabilize large-sizedperiodic textures (millimeter scale, see fig.1). The patterns have been characterized under optical and electronicmicroscopies. They result from the peculiar elastic and rheological properties of the graphene oxide liquid crystals.Our results also clarify why long-standing hypotheses on the presence of exotic phases [1] at large concentrationsare present in the literature.

Dye encapsulation into host single-walled carbon nanotubes is an easy way to create hybrid nano-systems with tunable opto-electronic properties. In this work, we will discuss the supramolecular organization inside the nanotube, the optical properties and the charge transfer as the function of the type of molecules, diameter and metallic or semiconducting character of the host nanotube. A significant electron transfer from encapsulated dyes to the carbon material is reported, whose magnitude strongly depends on the nanotube diameter, in good agreement with DFT calculations, and on the metallic or semiconducting character. Experiments also suggest a photo-activated electron transfer for small diameter (~9 Å) semiconducting and metallic tubes. Dye encapsulation is shown to significantly alter electron-phonon coupling into metallic nanotubes as revealed by the value of the coupling factor extracted from the Fano equation. The charge transfer is consistent with an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This charge transfer shifts the Fermi level, acting on the photoluminescence efficiency and the electron-phonon-coupling.