Active mechanisorption driven by pumping cassettes.

Over the past century, adsorption has been investigated extensively in equilibrium systems, with a focus on the van der Waals interactions associated with physisorption and electronic interactions in the case of chemisorption. In this study, we demonstrate mechanisorption, which results from nonequilibrium pumping to form mechanical bonds between the adsorbent and the adsorbate. This active mode of adsorption has been realized on surfaces of metal-organic frameworks grafted with arrays of molecular pumps. Adsorbates are transported from one well-defined compartment, the bulk, to another well-defined compartment, the interface, thereby creating large potential gradients in the form of chemical capacitors wherein energy is stored in metastable states. Mechanisorption extends, in a fundamental manner, the scope and potential of adsorption phenomena and offers a transformative approach to control chemistry at surfaces and interfaces.