Some porous crystalline solids change their structure upon guest inclusion. Unlocking the potential of these solids for a wide variety of applications requires full characterisation of the response to adsorption and the underlying framework–guest interactions. Here, we introduce an approach to understanding gas uptake in porous metal-organic frameworks (MOFs) by loading liquefied gases at GPa pressures inside the Zn-based framework ZIF-8. An integrated experimental and computational study using high-pressure crystallography, grand canonical Monte Carlo (GCMC) and periodic DFT simulations has revealed six symmetry-independent adsorption sites within the framework and a transition to a high-pressure phase. The cryogenic high-pressure loading method offers a different approach to obtaining atomistic detail on guest molecules. The GCMC simulations provide information on interaction energies of the adsorption sites allowing to classify the sites by energy. DFT calculations reveal the energy barrier of the transition to the high-pressure phase. This combination of techniques provides a holistic approach to understanding both structural and energetic changes upon adsorption in MOFs.

Raman spectroscopy and powder x-ray diffraction methods have been used to characterize a novel phase of nitrogen which forms on compression from ambient pressure at low temperatures. The new, λ, phase exhibits an exceptionally wide range of pressure stability from below 1 to 140 GPa, overlapping nine other known phases. On heating, its transformations are different to those observed in other phases, implying that the phase nitrogen adopts depends not only on P-T path, but also on the initial structural configuration, which greatly complicates its phase diagram.

We investigate the phase diagram of lithium at temperatures of 200 K to 400 K, to pressures over 100 GPa using X-ray diffraction in diamond anvil cells, covering the region in which the melting curve is disputed. To overcome degradation of the diamond anvils by dense lithium we utilize a rapid compression scheme taking advantage of the high flux available at modern synchrotrons. Our results show the hR1 and cI16 phases to be stable to higher temperature than previously reported. The melting minima of lithium is found to be close to room temperature between 40 GPa and 60 GPa, below which the solid is crystalline. Analysis of the stability fields of the cI16 and oC88 phases suggest the existence of a triple point between these and an undetermined solid phase at 60 GPa between 220 K and 255 K.

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