Molecular simulations using standard force fields have been carried out to model the adsorption of various light gases on a number of different metal organic framework-type materials. The results have been compared with the available experimental data to test the validity of the model potentials. We observe good agreement between simulations and experiments for a number of different cases and very poor agreement in other cases. Possible reasons for the discrepancy in simulated and measured isotherms are discussed. We predict hydrogen adsorption isotherms at 77 and 298 K in a number of different metal organic framework materials. The importance of quantum diffraction effects and framework charges on the adsorption of hydrogen at 77 K is discussed. Our calculations indicate that at room temperature none of the materials that we have tested is able to meet the requirements for on-board hydrogen storage for fuel cell vehicles. We have calculated the volume available in a given sorbent at a specified adsorption energy (density of states). We discuss how this density of states can be used to assess the effectiveness of a sorbent material for hydrogen storage.

We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a ‘hands-on’ approach, providing practical details and procedures as derived from literature as well as from the authors’ experience, in order to enable the reader to reproduce the results. Section is devoted to ‘bottom up’ approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section covers ‘top down’ techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers’ and modified Hummers’ methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by ...

We have improved the activation process for CuBTC [Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate] by extracting the N,N-dimethylformamide-solvated crystals with methanol; we identify material activated in this way as CuBTC−MeOH. This improvement allowed the activation to be performed at a much lower temperature, thus greatly mitigating the danger of reducing the copper ions. A review of the literature for H2 adsorption in CuBTC shows that the preparation and activation process has a significant impact on the adsorption capacity, surface area, and pore volume. CuBTC−MeOH exhibits a larger pore volume and H2 adsorption amount than any previously reported results for CuBTC. We have performed atomically detailed modeling to complement experimentally measured isotherms. Quantum effects for hydrogen adsorption in CuBTC were found to be important at 77 K. Simulations that include quantum effects are in good agreement with the experimentally measured capacity for H2 at 77 K and high pressure. However, simulations underpredict the amount adsorbed at low pressures. We have compared the adsorption isotherms from simulations with experiments for H2 adsorption at 77, 87, 175, and 298 K; nitrogen adsorption at 253 and 298 K; and argon adsorption at 298 and 356 K. Reasonable agreement was obtained in all cases.