A combined soft X-ray and theoretical investigation discloses the water harvesting behaviour of Mg-MOF-74 at the crystal surface

Metal–organic frameworks (MOFs) are receiving growing interest as transformative materials for real-world atmospheric water harvesting applications. However, obtaining molecular-level details on how surface effects regulate MOF water uptake has proven to be elusive. Here, we present a novel methodology based on ambient pressure soft X-ray absorption spectroscopy (AP-NEXAFS), machine learning-assisted theoretical spectroscopy and molecular dynamics simulations to gain selective insights into the behaviour of water at a MOF crystal surface. We applied our interdisciplinary method to investigate the structural and dynamical properties of water at the surface of the Mg-MOF-74 system, while obtaining complementary information on the water uptake and release from the bulk by synchrotron powder X-ray diffraction. Our investigation pointed out the simultaneous presence of Mg open sites and residual gas-phase water during dehydration, and proved that during water release a high number of surface Mg sites still interact with one or two water molecules. Conversely, when looking at the bulk, a significantly lower number of Mg sites have been found to interact with water molecules in the same experimental conditions. This behaviour suggests that the water adsorption (desorption) process starts from the interior of the material and propagates towards the channel openings. The combined approach based on AP-NEXAFS, PXRD experimental determinations and ML-supported theoretical analyses has been found to be a valuable tool to provide a thorough description of the water harvesting process at both surface and bulk of the crystal.