Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks
Developing O<sub>2</sub>-selective adsorbents that can produce high-purity oxygen from air remains a significant challenge. Here, we show that the chemically reduced metal–organic framework A<i><sub>x</sub></i>Fe<sub>2</sub>(BDP)<sub>3</sub> (A = Na<sup>+</sup>, K<sup>+</sup>; BDP<sup>2</sup><sup>−</sup> = 1,4-benzenedipyrazolate; 0 < <i>x</i> ≤ 2), which features coordinatively-saturated iron centers, is capable of strong and selective adsorption of O<sub>2</sub> over N<sub>2</sub> at ambient (25 °C) or even elevated (200 °C) temperature. Through a combination of gas adsorption measurements, single-crystal X-ray diffraction, and numerous spectroscopic probes, including <sup>23</sup>Na solid-state NMR and X-ray photoelectron spectroscopy, we demonstrate that selective O<sub>2</sub> uptake likely occurs as a result of outer-sphere electron transfer from the framework to form superoxide species, which are subsequently stabilized by intercalated alkali metal cations that reside in the one-dimensional triangular pores of the framework. The chemical reduction of a robust metal–organic framework to render it capable of binding O<sub>2</sub> through an outer-sphere electron transfer mechanism thus represents a promising and underexplored strategy for the design of next-generation O<sub>2</sub> adsorbents.