Hydrogen holds promise as a clean alternative automobile fuel, but its on-board storage presents significant challenges due to the low temperatures and/or high pressures required to achieve a sufficient energy density. The opportunity to significantly reduce the required pressure for high density H₂ storage persists for metal-organic frameworks due to their modular structures and large internal surface areas. The measurement of H₂ adsorption in such materials under conditions most relevant to on-board storage is crucial to understanding how these materials would perform in actual applications, although such data have to date been lacking. In the present work, the metal-organic frameworks M₂(m-dobdc) (M = Co, Ni; m-dobdc^4- = 4,6-dioxido-1,3-benzenedicarboxylate) and the isomeric frameworks M₂(dobdc) (M = Co, Ni; dobdc^4- = 1,4-dioxido-1,3-benzenedicarboxylate), which are known to have open metal cation sites that strongly interact with H₂, were evaluated for their usable volumetric H₂ storage capacities over a range of near-ambient temperatures relevant to on-board storage. Based upon adsorption isotherm data, Ni₂(m-dobdc) was found to be the top-performing physisorptive storage material with a usable volumetric capacity between 100 and 5 bar of 11.0 g/L at 25 °C and 23.0 g/L with a temperature swing between -75 and 25 °C. Additional neutron diffraction and infrared spectroscopy experiments performed with in situ dosing of D₂ or H₂ were used to probe the hydrogen storage properties of these materials under the relevant conditions. The results provide benchmark characteristics for comparison with future attempts to achieve improved adsorbents for mobile hydrogen storage applications.

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.

Coordinatively unsaturated metal sites within certain zeolites and metal-organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H₂ at the trigonal pyramidal Cu⁺ sites in the metal-organic framework Cu^I-MFU-4l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. The activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu⁺ coordination environment that enhances π-backbonding with H₂. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.