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Coordinatively unsaturated metal sites within certain zeolites and metal−organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electronpoor 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 H 2 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 H 2 . 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.

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The large-scale deployment of carbon capture technologies is expected to play a crucial role in efforts to meet stringent climate targets set forth by the Paris Agreement, but current models rely heavily upon carbon dioxide removal (CDR) strategies for which viability at the gigatonne scale is uncertain. While most 1.5 and 2 °C scenarios project rapid decarbonization of the energy sector facilitated by carbon capture and sequestration (CCS), they generally assume that CCS units can only capture ∼90% of the CO 2 in coal and natural gas combustion flues because this was previously considered the optimal condition for aqueous amine scrubbers. In this Perspective, we discuss a small but growing body of literature that examines the prospect of moving significantly beyond 90% capturea concept we term deep CCS in light of recent developments in materials and process design. The low incremental costs associated with performing varying degrees of deep CCS suggest that this approach is not only feasible but may also alleviate burdens placed upon CDR techniques facing significant barriers to large-scale deployment. We estimate that rapid deployment of deep CCS in deep decarbonization pathways could avoid more than 1 gigatonne of CO 2 globally each year. The principles of deep CCS could also be applied directly to the CDR strategy of employing bioenergy with CCS, which could lead to a significant alleviation of the land and freshwater burden associated with this technology.

This Perspective summarizes progress in the development of O2-selective metal–organic frameworks for adsorptive air separations and identifies key metrics and design considerations toward optimizing material performance for practical applications.